CN103347938B - Pre-preg, laminate board, printed wiring board, and semiconductor device - Google Patents

Pre-preg, laminate board, printed wiring board, and semiconductor device Download PDF

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Publication number
CN103347938B
CN103347938B CN201280006279.3A CN201280006279A CN103347938B CN 103347938 B CN103347938 B CN 103347938B CN 201280006279 A CN201280006279 A CN 201280006279A CN 103347938 B CN103347938 B CN 103347938B
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Prior art keywords
prepreg
aforementioned
resin
quality
glass
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CN103347938A (en
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大东范行
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Sumitomo Bakelite Co Ltd
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Sumitomo Bakelite Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/14—Semiconductor wafers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0275—Fibers and reinforcement materials
    • H05K2201/029—Woven fibrous reinforcement or textile

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Textile Engineering (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

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

Description

Prepreg, veneer sheet, printed circuit board (PCB) and semiconductor device
Technical field
The present invention relates to prepreg, veneer sheet, printed circuit board (PCB) and semiconductor device.
Background technology
In recent years, along with the requirement of multifunction of electronics etc., the quickenings such as the high-density integrated of electronic unit and high-density installation.Therefore,, for the printed circuit board (PCB) of the reply high-density installation wherein used, require the miniaturization of wiring and the downsizing of through hole and via.
Through hole and via can form with laser such as drilling machine, carbon dioxide lasers, and particularly the punching of minor diameter can be used laser.In the perforation processing of utilizing laser to carry out, form insulation layer wall concavo-convex larger in hole, aperture, shape more easily produce deviation, and working accuracy reduces.
The insulation layer of printed circuit board (PCB) can form by 1 prepreg or the overlapping prepreg of multi-disc are carried out to heating and pressurizing.Generally, prepreg can be made by the following method, that is, make to contain in the base material impregnation solvents such as woven fiber glass and take the varnish that resin combination that thermosetting resin is main component forms, and it is heated and makes it dry, makes thus.Utilizing laser processing to form in the insulation layer wall in hole, in base material part and resin combination part, utilize the meltbility of laser there are differences.Therefore,, when the little and hole of the density of base material is thick, there are aperture, shape easily to produce the tendency of deviation.On the other hand, by using compact highdensity base material, can improve the perforation processing (patent documentation 1,2) that insulation layer utilizes laser.
In addition, the densification of installing in order to tackle parts on printed circuit board (PCB), requires to reduce warpage that printed circuit board (PCB) causes because of thermal expansion to guarantee connection reliability.Semiconductor device (semiconductor package body) semiconductor element mounted thereon on printed circuit board (PCB) forms, and the coefficient of thermal expansion of semiconductor element is 3～6ppm/ ℃, less with the coefficient of thermal expansion of printed circuit board (PCB) than general semiconductor package.Therefore,, when semiconductor package body is applied to thermal shocking, semiconductor packages is known from experience and with the thermal expansion rate variance of printed circuit board (PCB), warpage to be occurred because of semiconductor element and semiconductor package body sometimes.At this moment, between semiconductor element and semiconductor package body are with printed circuit board (PCB), between semiconductor package body and the printed circuit board (PCB) installed, there is sometimes bad connection.
By the little insulativity material of coefficient of thermal expansion is used for to insulation layer, can reduce the warpage that printed circuit board (PCB) causes because of thermal expansion.In order to make to become the prepreg low linear expansion of insulativity material, as the resin combination for the manufacture of prepreg, can use the highly-filled resin combination (patent documentation 3) that has inorganic filling material.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2001-38836 communique
Patent documentation 2: TOHKEMY 2000-22302 communique
Patent documentation 3: TOHKEMY 2009-138075 communique
Summary of the invention
Yet when using highdensity base material to make prepreg, resin combination is poor to the impregnation of base material, especially contains the resin combination of a large amount of packing materials, because packing material does not enter the impregnation that is difficult to carry out resin combination between the fiber of base material.In addition, in order to improve impregnation, when reducing the content etc. of packing material, be sometimes difficult to maintain other various characteristics that prepreg has.
The present invention completes in order to address the above problem, and the object of the invention is to, and provides and can maintain various characteristics and the prepreg of compositions of thermosetting resin to the impregnation excellence of fiber weaving cloth that prepreg has.In addition, the object of the invention is to, provide and use the metal-coated laminated board of this prepreg and use printed circuit board (PCB) and the semiconductor device that they obtain.
According to the present invention, a kind of prepreg can be provided, it is the prepreg that the fiber weaving cloth impregnation resin combination that makes to consist of precursor (strand) forms, and in aforementioned precursor, has silica dioxide granule.
According to the present invention, can provide and can maintain various characteristics and the prepreg of compositions of thermosetting resin to the impregnation excellence of fiber weaving cloth that prepreg has.
In addition, according to the present invention, can use aforementioned prepreg and/or use the metal-coated laminated board of manufacturing with aforementioned prepreg to manufacture printed circuit board (PCB) and semiconductor device.
Accompanying drawing explanation
Preferred implementation and subsidiary the following drawings thereof by the following stated can further clear and definite above-mentioned purpose and other object, feature and advantages.
Fig. 1 means the sketch chart of an example of the manufacture method of metal-coated laminated board of the present invention.
Fig. 2 means the sketch chart of an other example of the manufacture method of metal-coated laminated board of the present invention.
Fig. 3 is the photo of the sectional view of the prepreg that obtains of embodiment 1.
Fig. 4 is the photo of the sectional view of the prepreg that obtains of comparative example 4.
Fig. 5 be metal-coated laminated board that embodiment 1 is obtained the whole facet etch of Copper Foil surperficial photo.
Fig. 6 be metal-coated laminated board that comparative example 6 is obtained the whole facet etch of Copper Foil surperficial photo.
Fig. 7 is the SEM photo of the enlarged view in the space observed in Fig. 6.
Fig. 8 is the SEM photo of enlarged view of the section in the space observed in Fig. 7.
Fig. 9 means the SEM photo of sectional view of a part of precursor of the fiber weaving cloth that forms the prepreg that embodiment 1 obtains.
Figure 10 means the SEM photo of sectional view of a part of precursor of the fiber weaving cloth that forms the prepreg that embodiment 1 obtains.
Figure 11 means the SEM photo of sectional view of a part of precursor of the fiber weaving cloth that forms the prepreg that embodiment 1 obtains.
Figure 12 means the SEM photo of sectional view of a part of precursor of the fiber weaving cloth that forms the prepreg that embodiment 1 obtains.
Embodiment
Below, at length prepreg of the present invention, metal-coated laminated board, printed circuit board (PCB) and semiconductor device are described.
1. prepreg
Prepreg of the present invention is the prepreg that the fiber weaving cloth impregnation resin combination that makes to consist of precursor forms.In addition, in the precursor of formation fiber weaving cloth, there is silica dioxide granule.It should be noted that, precursor is the fibrous bundle that forms fiber weaving cloth.By precursor being woven to become braiding structure described later, form fiber weaving cloth.
The inventor finds, while existing silica dioxide granule to form prepreg, can maintain the various characteristics that prepreg has in precursor, and can improve the impregnation of resin combination to fiber weaving cloth.Here, various characteristics refers to insulating reliability, the laser processing of prepreg or the low heat expansion property of prepreg etc. such as printed circuit board (PCB) described later.
When resin combination is good to the impregnation of fiber weaving cloth, in the prepreg that can suppress to obtain, produce space.Thus, at insulation layer, use in the printed circuit board (PCB) of this prepreg, can seek to improve insulating reliability.
In addition, even when using highdensity fiber weaving cloth, also can obtain higher impregnation.Therefore, use highdensity fiber weaving cloth, can form the prepreg of laser processing excellence.
And then, by improving the impregnation of resin combination to fiber weaving cloth, can fill packing material at fiber weaving cloth inner height.Therefore, can seek the low-thermal-expansion of prepreg.Thus, can suppress insulation layer uses the printed circuit board (PCB) of this prepreg to produce warpage.Thereby, can improve the connection reliability of semiconductor device.
The resin combination that forms prepreg is for the compositions of thermosetting resin that at least comprises thermosetting resin and packing material is (below sometimes referred to as " resin combination ".）。
For the resin combination that forms prepreg, the silica dioxide granule that for example ratio of preferred 1～20 quality % with packing material contains median size 5～100nm.The inventor finds, even the prepreg that resin combination that highdensity fiber weaving cloth impregnation contains a large amount of packing materials is obtained, by the silica dioxide granule that makes aforementioned packing material contain median size 5～100nm with the ratio of 1～20 quality %, the impregnation of resin combination is also good.Think that this is because, the silica dioxide granule of aforementioned median size 5～100nm enters between the fiber of fiber weaving cloth, is in precursor and make between fiber to expand, so the packing material beyond the silica dioxide granule of median size 5～100nm also can enter fiber weaving cloth.So,, by using the silica dioxide granule of nano-scale of median size 5～100nm as packing material, can obtain having in precursor the prepreg of silica dioxide granule.
In addition, the surface potential of the silica dioxide granule of median size 5～100nm is different from the surface potential of other packing material, so the silica dioxide granule of median size 5～100nm and aforementioned packing material attract because of interaction.Therefore, the silica dioxide granule of median size 5～100nm is present in aforementioned packing material around, and the silica dioxide granule of median size 5～100nm has the effect of spacer.So, the silica dioxide granule of median size 5～100nm is present in aforementioned packing material around, as spacer, works, and thus, the power of attracting each other of being brought by Van der Waals force of aforementioned packing material is reduced, and prevents cohesion.Thus, aforementioned packing material becomes more high dispersion state, can prevent that mobility from reducing.
The silica dioxide granule of aforementioned median size 5～100nm is preferably used to be dispersed in advance the form of the slurry forming in organic solvent.Thus, can improve the dispersiveness of packing material, the mobility occurring in the time of can suppressing to use other packing material reduces.Think that it be the reasons are as follows.First, the particle of the nano-scale that the silicon-dioxide of nano-scale is such easily condenses, and often forms 2 aggregates etc. while being compounded in resin combination, by using the particle of pulp-like, can prevent 2 times such cohesions, can prevent that the mobility causing thus from reducing.In addition, for for packing material of the present invention, in order to prevent cohesion and to improve dispersiveness, preferably implement in advance surface treatment.
It should be noted that, so-called highdensity fiber weaving cloth in the present invention, refers to and not only increases the filling density of yarn radical, and has carried out in heterogeneity by the high fiber weaving cloth of opening fibrillation, making the processing such as thickness reduction by flattening of every 1 fiber.The volume density of highdensity fiber weaving cloth is for example 1.05g/cm 3above.Thus, impregnation resin combination between every 1 fiber can be further made, the highly-filled of packing material can be further sought.And then, owing to can fully guaranteeing the amount of resin on fiber weaving cloth, therefore, the formability when can maintain lamination Copper Foil on prepreg and making copper-clad laminate or while making the surface smoothing of copper-clad laminate.
So, prepreg of the present invention is because resin combination is good to the impregnation of fiber weaving cloth, and therefore, the space of generation is few.In addition, therefore owing to containing a large amount of packing materials in resin combination, be low heat expansion property, use the warpage of the printed circuit board (PCB) that prepreg of the present invention obtains little.It should be noted that, in the present invention, the thermal expansivity of prepreg is the thermal expansivity of instigating under the state that prepreg solidified.
In addition, prepreg of the present invention is by highly-filled packing material, excellent heat resistance and be high rigidity.And then the volume density that forms the fiber weaving cloth of prepreg of the present invention is preferably 1.05～1.30g/cm 3.By using volume density, be 1.05～1.30g/cm 3highdensity fiber weaving cloth like this, when as the insulation layer of printed circuit board (PCB), by laser processing, can form the precision of aperture and shape good and can suppress the outstanding hole of fiber.
In addition, generally, for the prepreg that the resin combination that contains a large amount of packing materials for use obtains, because resin combination worsens the impregnation of base material, therefore, base material is difficult to keep resin combination with uniform thickness, when this prepreg is made to printed circuit board (PCB) for insulation layer, exists the surface smoothness of aforementioned dielectric layer poor,, the problem that be difficult to carry out fine wiring processing and so on poor with the adaptation of conductor layer.These problems may further worsen when making prepreg slimming.On the other hand, for prepreg of the present invention, because resin combination is good to the impregnation of fiber weaving cloth, therefore, fiber weaving cloth can keep resin combination with uniform thickness, surface smoothness, good with the adaptation of conductor layer, and can tackle slimming.In addition, the resin combination that prepreg of the present invention contains a large amount of packing materials by use becomes high heat resistance, high rigidity.
First, the fiber weaving cloth using in the present invention is described.
As the fiber weaving cloth using in the present invention, be not particularly limited, for example, can enumerate the fiber weaving cloth being formed by synthon, steel fiber, carbon fiber, mineral fibre etc. such as glass fibre, aramid fiber (aramid), polyester, aromatic polyester, fluoro-resin.Wherein, owing to being low heat expansion property, high rigidity and excellent in dimensional stability, therefore, the glass fibre preferably being formed by glass fibre is weaved cotton cloth.
Aforementioned glass fibre is not particularly limited, preferably at least with the ratio of 50 quality %～100 quality %, contains SiO 2, with the ratio of 0 quality %～30 quality %, contain Al 2o 3, with the ratio of 0 quality %～30 quality %, contain CaO, particularly preferably use and select free T glass (sometimes also referred to as " S glass ".), at least a kind of glass in the group that forms of D glass, E glass, NE glass, silica glass forms, wherein, more preferably T glass (S glass), silica glass, D glass,, high strength, more preferably T glass (S glass), silica glass excellent from the viewpoint of low heat expansion property.
It should be noted that, in the present invention, T glass (S glass) is the glass of the composition that contains following material with following ratio: SiO 2be 62 quality %～65 quality %, Al 2o 3be that 20 quality %～25 quality %, CaO are that 0 quality %～0.01 quality %, MgO are 10 quality %～15 quality %, B 2o 3be 0 quality %～0.01 quality %, Na 2o and K 2o adds up to 0 quality %～1 quality %; D glass is the glass of the composition that contains following material with following ratio: SiO 2be 72 quality %～76 quality %, Al 2o 3be that 0 quality %～5 quality %, CaO are that 0 quality %～1 quality %, MgO are 0 quality %～1 quality %, B 2o 3be 20 quality %～25 quality %, Na 2o and K 2o adds up to 3 quality %～5 quality %; E glass is the glass of the composition that contains following material with following ratio: SiO 2be 52 quality %～56 quality %, Al 2o 3be that 12 quality %～16 quality %, CaO are that 15 quality %～25 quality %, MgO are 0 quality %～6 quality %, B 2o 3be 5 quality %～10 quality %, Na 2o and K 2o adds up to 0～0.8 quality %; NE glass is the glass of the composition that contains following material with following ratio: SiO 2be 52 quality %～56 quality %, Al 2o 3be that 10 quality %～15 quality %, CaO are that 0 quality %～10 quality %, MgO are 0 quality %～5 quality %, B 2o 3be 15 quality %～20 quality %, Na 2o and K 2o adds up to 0 quality %～1 quality %, TiO 2be 0.05 quality %～5 quality %, silica glass is that the ratio with 99.0 quality %～100 quality % contains SiO 2the glass of composition.
Aforementioned glass fibre is not particularly limited, preferably to make Young's modulus when tabular be 50～100GPa, make tensile strength when tabular is that 25GPa tensile strength above, the length direction while making fiber weaving cloth is more than 30N/25mm, and more preferably to make Young's modulus when tabular be 80～100GPa, make tensile strength when tabular is that 35GPa tensile strength above, the length direction while making fiber weaving cloth is more than 45N/25mm.Thus, can obtain the prepreg of excellent in dimensional stability.It should be noted that, aforementioned Young's modulus is the value of utilizing common used known three point bending test machine to measure according to JIS R1602, aforementioned tensile strength is that according to JIS R3420, to utilize the value of common the used tension type stretching test machine determination of known constant speed, the tensile strength of aforementioned length direction be according to JISR3420, glass fibre to be made and weaved cotton cloth and the value of utilization and the aforementioned same tension type stretching test machine determination of constant speed.
It should be noted that, in the mensuration of aforementioned Young's modulus and the mensuration of aforementioned tensile strength, " tabular " refers to and will make the state of the sheet glass of thickness 0.5～1.0mm with the glass composition of glass fibre same composition.In addition, in the mensuration of the tensile strength of aforementioned length direction, " length direction " refers to organizine (vertical yarn) direction.
Aforementioned glass fibre is not particularly limited, the thermal expansivity of the organizine direction of measuring according to JIS R3102 be preferably 10ppm/ ℃ following, be particularly preferably below 3ppm/ ℃.Can reduce the warpage that printed circuit board (PCB) causes because of thermal expansion thus.
The thickness that aforementioned fibers is weaved cotton cloth is not particularly limited, and is preferably 10～200 μ m, more preferably 10～140 μ m, 20～90 μ m more preferably.Thus, resin combination becomes well to the impregnation of fiber weaving cloth, can also tackle slimming.
The volume density that aforementioned fibers is weaved cotton cloth is preferably 1.05～1.30g/cm 3, be particularly preferably 1.10～1.25g/cm 3.When volume density is during lower than aforementioned lower value, the laser processing of insulation layer is poor, and when volume density surpasses aforementioned higher limit, resin combination worsens the impregnation of fiber weaving cloth.It should be noted that, by the filling density radical of adjusting organizine and tram, through opening the thickness of the fiber of fine flat processing, regulate the volume density of fiber weaving cloth.
Aforementioned fibers is weaved cotton cloth and is not particularly limited, and Gas permeability is preferably 1～80cc/cm 2/ sec, be particularly preferably 3～50cc/cm 2/ sec.When Gas permeability is during lower than aforementioned lower value, resin combination worsens the impregnation of fiber weaving cloth, and when Gas permeability surpasses aforementioned higher limit, the laser processing of insulation layer is poor.
Aforementioned fibers is weaved cotton cloth and is not particularly limited, and mass area ratio is preferably 10～160g/m 2, be particularly preferably 15～130g/m 2.When mass area ratio is during lower than aforementioned lower value, the low heat expansion property of prepreg is poor, and when mass area ratio surpasses aforementioned higher limit, resin combination worsens the impregnation of fiber weaving cloth, or the laser processing of insulation layer is poor.
In addition, aforementioned fibers middle the used fiber of weaving cotton cloth is not particularly limited, flat ratio is preferably 1:2～1:50, is particularly preferably 1:5～1:30.Flat ratio by the fiber that makes to use in fiber weaving cloth is in aforementioned range, and the impregnation wettability that resin combination is weaved cotton cloth to aforementioned fibers is more excellent, thereby can improve the insulating reliability between through hole, and improves the laser processing of insulation layer.It should be noted that, in the present invention, flat ratio is the thickness with silk: the value of the width means of silk.
In addition, the braiding structure that aforementioned fibers is weaved cotton cloth is not particularly limited, for example, can enumerate braiding structures such as plain weave, square flat sennit are knitted, satin weave, twill weave etc., wherein, excellent from the viewpoint of the layer insulation reliability of laser processing, intensity, via, be preferably plain weave structure.
Secondly, the compositions of thermosetting resin using in the present invention is described.
The compositions of thermosetting resin using in the present invention at least comprises thermosetting resin and packing material.Ratio with 50～85 quality % of the solids component of aforementioned compositions of thermosetting resin contains aforementioned packing material.In addition, the silica dioxide granule that aforementioned compositions of thermosetting resin contains median size 5～100nm with the ratio of 1～20 quality % of aforementioned packing material.And then aforementioned compositions of thermosetting resin can also comprise solidifying agent, coupling agent etc. as required.
(packing material)
The silica dioxide granule that aforementioned packing material contains median size 5～100nm with the ratio of 1～20 quality % of aforementioned packing material integral body.
As aforementioned silica dioxide granule, be not particularly limited, for example, can use the Combustion by VMC(Vaporized Metal) method, PVS(Physical Vapor Synthesis) silica dioxide granule manufactured of the combustion method such as method, the methods such as scorification, the precipitator method, gel method of flame melting that broken silicon-dioxide is carried out.Wherein, VMC method particularly preferably.Aforementioned VMC method is in the chemical flame by forming, to drop into Si powder to make to carry out the cooling method that forms silicon dioxide microparticle after its burning in oxygen-containing gas.In aforementioned VMC method, the particle diameter of the Si powder dropping into by adjusting, input amount, flame temperature etc., can regulate the particle diameter of the silica micro-particle obtaining.In addition, as aforementioned silica dioxide granule, can also use NSS-5N(Tokuyama Corporation to manufacture), Sicastar43-00-501(Micromod Partikeltechnologie GmbH manufactures) etc. commercially available product.
For the silica dioxide granule of aforementioned median size 5～100nm, from the viewpoint of impregnation, especially particularly preferably median size is 10～75nm.Think, the median size of silica dioxide granule is during lower than 5nm, between the fiber of can not expansion fiber weaving cotton cloth, in addition, while being greater than 100nm, sometimes can not enter between fiber.
The median size of aforementioned silica dioxide granule can be measured by such as laser diffraction and scattering method and dynamic light scattering method etc.In the situation that the silica dioxide granule of aforementioned median size 5～100nm, in water, utilize ultrasonic wave that particle is disperseed, utilize dynamic light scattering formula particle size distribution device (HORIBA manufacture, LB-550), with volume reference instrumentation, determine the size-grade distribution of particle, its median particle diameter (D50) is made as to median size.
In addition, aforementioned silica dioxide granule is not particularly limited, is preferably hydrophobicity.Thus, can suppress silica dioxide granule cohesion, can make silica dioxide granule be dispersed in well in resin combination of the present invention.In addition, due to the affinity raising of thermosetting resin and silica dioxide granule, the surperficial adaptation of aforementioned hot thermosetting resin and aforementioned silica dioxide granule improves, and therefore, can obtain the insulation layer of physical strength excellence.
As making silica dioxide granule, be hydrophobic method, for example, can enumerate silicane and/or the alkyl silazane class of Yong Han functional group in advance silica dioxide granule is carried out to surface-treated method etc.As the aforementioned silicane containing functional group, can use known material, for example, can enumerate epoxy silane, aminosilane, vinyl silanes, acrylic acid or the like silane, hydrosulphonyl silane, isocynate silane, thioether silane, ureido silane etc.As aforesaid alkyl silazane class, for example, can enumerate hexamethyldisilazane (HMDS), 1,3-divinyl-1,1,3,3-tetramethyl-disilazane, prestox three silazane, pregnancy basic ring three silazane etc.In addition, by silica dioxide granule is carried out to aforementioned surfaces processing, also can bring into play and prevent packing material cohesion and improve dispersed effect.
For in advance aforementioned silica dioxide granule being carried out to surface-treated containing the silicane of functional group and/or the amount of alkyl silazane class, be not particularly limited, with respect to aforementioned silica dioxide granule 100 weight parts, be preferably 0.01 weight part above and be below 5 weight parts.More preferably 0.1 weight part is above and be below 3 weight parts.When the content of the silicane of Dang Han functional group and/or alkyl silazane class surpasses aforementioned higher limit, when manufacturing printed circuit board (PCB), insulation layer can crack sometimes, and during lower than aforementioned lower value, the bonding force of resinous principle and silica dioxide granule reduces sometimes.
For silicane and/or the alkyl silazane class of Yong Han functional group in advance, aforementioned silica dioxide granule is carried out to surface-treated method, be not particularly limited, be preferably wet type mode or dry type mode.Be particularly preferably wet type mode.Wet type mode is compared with dry type mode, can to the surface of aforementioned silica dioxide granule, process equably.
In addition, preferably contrast table area more than 50% carry out aforementioned surfaces processing.
The silica dioxide granule that contains aforementioned median size 5～100nm with the ratio of 1～20 quality % of packing material integral body.When content is during lower than aforementioned lower value, the effect that improves impregnation is insufficient, when content surpasses aforementioned higher limit, on the contrary, worries that impregnation worsens, the insufficient formability of prepreg.It should be noted that, the content of the silica dioxide granule of aforementioned median size 5～100nm is 3～15 quality % of packing material integral body more preferably.
For the packing material using in the present invention, except the silica dioxide granule of aforementioned median size 5～100nm, be not particularly limited, can contain such as: talcum, calcined clay, the silicate such as calcined clay, mica, glass not; Titanium oxide, aluminum oxide, median size are greater than the oxide compounds such as silica dioxide granule of 100nm; The carbonate such as calcium carbonate, magnesiumcarbonate, hydrotalcite; Aluminium hydroxide, boehmite (AlO (OH), are commonly referred to boehmite (that is, the Al of " vacation " boehmite 2o 3xH 2o, here, x=1～2)), the metal hydroxides such as magnesium hydroxide, calcium hydroxide; Vitriol or the sulphite such as barium sulfate, calcium sulfate, calcium sulfite; The borates such as zinc borate, barium metaborate, aluminum borate, lime borate, Sodium Tetraborate; The nitride such as aluminium nitride, boron nitride, silicon nitride, carbonitride; The inorganic filling materials such as the titanate such as strontium titanate, barium titanate.For aforementioned inorganic filling material, can use separately wherein a kind, also two or more kinds may be used.Wherein, be preferably spherical silicon dioxide particle, talcum, fired talc, aluminum oxide that magnesium hydroxide, aluminium hydroxide, boehmite, median size are greater than 100nm, aspect low heat expansion property, impregnation, be particularly preferably spherical silicon dioxide particle, spherical alumina that boehmite, median size are greater than 100nm.
As the inorganic filling material beyond the silica dioxide granule of aforementioned median size 5～100nm, (be sometimes referred to as below " other inorganic filling material ".), be not particularly limited, can use the monodispersed inorganic filling material of median size, also can use the polydisperse inorganic filling material of median size.And then, also can be used together one kind or two or more median size list and disperse and/or polydisperse inorganic filling material.In the present invention, median size is for referring to that the standard deviation of particle diameter is below 10% single dispersion, and polydispersion refers to that the standard deviation of particle diameter is more than 10%.
Median size to aforementioned other inorganic filling material is not particularly limited, and is preferably 0.1 μ m～5.0 μ m, is particularly preferably 0.1 μ m～3.0 μ m.When the particle diameter of other inorganic filling material is during lower than aforementioned lower value, because the viscosity of resin combination uprises, therefore, the workability when making prepreg is brought impact sometimes.In addition, when surpassing aforementioned higher limit, occur in sometimes in resin combination the phenomenons such as inorganic filling material precipitation.It should be noted that, median size can be used laser diffraction/diffuse transmission type particle size distribution device (common equipments such as SALD-7000 that Shimadzu Seisakusho Ltd. manufactures) to measure.
And then, carrying out the processing of diameter holes, the processing of the narrow pitch in hole and fine rule add man-hour, preferably aforementioned other inorganic filling material is carried out to coarse grain and cut (coarse particle cut).Wherein, the coarse grain preferably carrying out more than 45 μ m is cut, and the coarse grain further preferably carrying out more than 20 μ m is cut, and the coarse grain particularly preferably carrying out more than 10 μ m is cut.It should be noted that, " coarse grain is cut " refers to the big or small coarse particles of getting rid of more than described particle diameter.
In addition, for the packing material using in the present invention, preferably except aforementioned inorganic filling material, also contain the organic filler materials such as rubber grain etc.As the preference of operable rubber grain in the present invention, can enumerate core-shell-type rubber grain, crosslink propylene nitrile divinyl rubber particle, cross-linked styrene divinyl rubber particle, acrylic rubber particle, organic silicon granule etc.
Core-shell-type rubber grain is the rubber grain with sandwich layer and shell, for example, can enumerate: outer field shell is by the rubber grain of 2 layers of structure that glassy polymers forms, the sandwich layer of internal layer consists of rubbery polymer; Or outer field shell by glassy polymers form, middle layer is by rubber grain of the 3-tier architecture that rubbery polymer forms, sandwich layer consists of glassy polymers etc.Glassy polymers layer such as the polymkeric substance by methyl methacrylate etc. forms, and rubbery polymer layer is such as by formations such as butyl acrylate things (isoprene-isobutylene rubber).As the concrete example of core-shell-type rubber grain, can enumerate: Sutafiroido AC3832, AC3816N(trade(brand)name, Ganz Chemical Co., Ltd. manufactures), METABLEN KW-4426(trade(brand)name, Mitsubishi Rayon Co., Ltd. manufactures).As the concrete example of crosslink propylene nitrile divinyl rubber (NBR) particle, can enumerate XER-91(median size 0.5 μ m, JSR Corporation and manufacture) etc.
As the concrete example of cross-linked styrene divinyl rubber (SBR) particle, can enumerate XSK-500(median size 0.5 μ m, JSR Corporation and manufacture) etc.As the concrete example of acrylic rubber particle, can enumerate: METABLEN W300A(median size 0.1 μ m), W450A(median size 0.2 μ m) (Mitsubishi Rayon Co., Ltd. manufacture) etc.
For aforementioned organic silicon granule, so long as the caoutchouc elasticity particulate being formed by organopolysiloxane, be not particularly limited, for example, can enumerate: the particulate itself being formed by organo-silicone rubber (organopolysiloxane cross-linked elastomer) and the core shell structure particle that forms with the core that the silicone covering of three-dimensional cross-linked type main body is formed by the organosilicon of the crosslinked main body of two dimension etc.As aforementioned organic silicon granule, can use: KMP-605, KMP-600, KMP-597, KCC of KMP-594(SHIN-ETSU HANTOTAI manufacture), Trefil E-500, Trefil E-600(Dow Corning Toray Co., Ltd. manufactures) etc. commercially available product.
In packing material used in the present invention, the packing material beyond the silica dioxide granule that is 5～100nm for median size, in order to prevent cohesion and to improve dispersiveness, preferably implements surface treatment in advance.Surface treatment agent can be used known silane coupling agent, for example, can enumerate: epoxy silane, aminosilane, vinyl silanes, acrylic acid or the like silane, hydrosulphonyl silane etc.In addition, preferably contrast table area more than 50% carry out surface treatment.
For the content of the packing material in resin combination used in the present invention, in the solids component benchmark of resin combination integral body, be preferably 50～85 quality %, be particularly preferably 65～75 quality %.When packing material content surpasses aforementioned higher limit, the non-constant of mobility of resin combination, the workability while manufacturing prepreg is poor.When packing material content is during lower than above-mentioned lower value, coefficient of thermal expansion is high sometimes, and the intensity of insulation layer is insufficient.
(thermosetting resin)
As aforementioned hot thermosetting resin, be not particularly limited, can use epoxy resin, cyanate ester resin, bimaleimide resin, resol, benzoxazine colophony, vinyl benzyl ether resin, benzocyclobutane olefine resin etc., generally, appropriately combined other thermosetting resin of epoxy resin is used.
As aforementioned epoxy resins, be not particularly limited, be preferably in fact the not epoxy resin of halogen atom.Here, so-called " in fact not halogen atom ", even if refer to that the halogen that allows to come from the halogen set member using in the building-up process of epoxy resin removes operation through halogen and still remain in epoxy resin.Generally, in preferred epoxy containing surpass 30ppm halogen atom.
As the aforementioned in fact epoxy resin of halogen atom not, for example can enumerate: bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol E-type epoxy resin, bisphenol-s epoxy resin, bisphenol Z type epoxy resin (4, 4 '-hexylidene hexichol phenol-type epoxy resin, 4, 4 '-cyclohexydiene bisphenol type epoxy resin), bis-phenol P type epoxy resin (4, 4 '-(1, 4)-phenylene di-isopropyl) hexichol phenol-type epoxy resin, 4, 4 '-(1, 4)-phenylene diisopropylidene) bisphenol type epoxy resin), bis-phenol M type epoxy resin (4, 4 '-(1, 3-phenylene di-isopropyl) hexichol phenol-type epoxy resin) bisphenol-type epoxy resin such as, the phenolic resin varnish type epoxy resins such as phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, biphenyl type epoxy resin, xylol type epoxy resin, phenol aralkyl-type epoxy resin, biphenyl aralkyl-type epoxy resin, biphenyl dimethylene type epoxy resin, tris-phenol phenolic resin varnish type epoxy resin, 1,1,2,2-(, tetra-phenol) the Racemic glycidol ethers of ethane, 3 officials can or 4 officials can the aryl alkylene type epoxy resin such as glycidyl amine, tetramethyl biphenyl type epoxy resin, the naphthalene type epoxy resin such as naphthalene framework modification epoxy resin, methoxynaphthalene modification cresols phenolic resin varnish type epoxy resin, methoxynaphthalene dimethylene type epoxy resin, naphthylidene ether type epoxy, anthracene type epoxy resin, phenoxy group type epoxy resin, dicyclopentadiene-type epoxy resin, norbornene-type epoxy resin, diamantane type epoxy resin, fluorenes type epoxy resin, fire-retardantization epoxy resin that above-mentioned epoxy resin halogenation is obtained etc.
Both can use separately a kind of epoxy resin in these epoxy resin, also can be used together two or more epoxy resin with different weight-average molecular weight, can also and with the prepolymer of one kind or two or more epoxy resin and epoxy resin.
In these epoxy resin, particularly preferably select at least a kind in the group that free biphenyl dimethylene type epoxy resin, phenolic resin varnish type epoxy resin, naphthalene modification cresols phenolic resin varnish type epoxy resin and anthracene type epoxy resin forms.By using these epoxy resin, can improve the veneer sheet that obtains and moisture absorption solder heat resistance and the flame retardant resistance of printed circuit board (PCB).
In addition, in these epoxy resin, by using naphthylidene ether type epoxy, can improve the veneer sheet that obtains and thermotolerance, low heat expansion property and the low thermal shrinkage behavior of printed circuit board (PCB).
Naphthylidene ether type epoxy can use-case represents as following general formula (1).
[Chemical formula 1]
(in formula, R 1represent hydrogen atom or methyl, R 2represent independently respectively the alkyl, aralkyl, naphthyl of hydrogen atom, carbonatoms 1～4 or containing the naphthyl of glycidyl ether, o and m are respectively 0～2 integer, and any in o or m is more than 1.）
Content to aforementioned epoxy resins is not particularly limited, and the solids component benchmark in aforementioned resin integral body, is preferably 5～60 % by weight.When content is during lower than aforementioned lower value, the solidified nature of resin combination reduces sometimes, or uses prepreg that this resin combination obtains or the wet fastness of printed circuit board (PCB) to reduce.In addition, when content surpasses aforementioned higher limit, the linear thermal expansion ratio of prepreg or printed circuit board (PCB) becomes large sometimes, or thermotolerance reduces.In the solids component benchmark of resin combination integral body, the content of aforementioned epoxy resins is particularly preferably 10～50 % by weight.
Weight-average molecular weight to aforementioned epoxy resins is not particularly limited, and is preferably 1.0 * 10 2～2.0 * 10 4.When weight-average molecular weight is during lower than aforementioned lower value, the surface of prepreg produces viscosity sometimes, and when weight-average molecular weight surpasses aforementioned higher limit, the solder heat resistance of prepreg reduces sometimes.By weight-average molecular weight is made as in aforementioned range, can make the balance of these characteristics excellent.
In the present invention, the weight-average molecular weight of aforementioned epoxy resins can be measured with for example gel permeation chromatography (GPC), next specific with the weight molecular weight of polystyrene conversion.
Aforementioned resin is not particularly limited, by comprising cyanate ester resin, can improves flame retardant resistance, reduce thermal expansivity, and then, the electrical characteristic (low-k, low dielectric loss angle tangent) of prepreg etc. can be improved.
Aforementioned cyanate ester resin is not particularly limited, for example, can by use halogen cyan compound is reacted with phenol or aphthols and as required the method such as heating carry out pre-polymerization materialization and obtain.In addition, the commercially available product that also can use such operation to prepare.
Kind as aforementioned cyanate ester resin, is not particularly limited, and for example, can enumerate the bisphenol type cyanate ester resins such as phenolic varnish type cyanate ester resin, bisphenol A cyanate ester resin, bisphenol E-type cyanate resin, tetramethyl bisphenol F cyanate resin etc.
For aforementioned cyanate ester resin, preferably in molecule, have 2 above cyanate ester based (O-CN).For example, can enumerate: 2,2 '-bis-(4-cyanate radical closes phenyl) isopropylidene (2,2 '-bis(4-cyanatophenyl) isopropylidene), 1,1 '-bis-(4-cyanate radical closes phenyl) ethane, two (4-cyanate radical closes-3,5-3,5-dimethylphenyl) methane, 1,3-two (4-cyanate radical closes phenyl-1-(1-methyl ethidine)) benzene, dicyclopentadiene-type cyanate, phenol phenolic varnish type cyanate, two (4-cyanate radical closes phenyl) thioether, two (4-cyanate radical closes phenyl) ether, 1,1,1-tri-(4-cyanate radical closes phenyl) ethane, three (4-cyanate radical closes phenyl) phosphorous acid ester, two (4-cyanate radical closes phenyl) sulfone, two (4-cyanate radical the closes phenyl) propane of 2,2-, 1,3-, Isosorbide-5-Nitrae-, 1,6-, 1,8-, 2,6-or 2,7-, bis-cyanate radicals close naphthalene, 1,3,6-, tri-cyanate radicals close naphthalene, 4,4-, bis-cyanate radicals close biphenyl, and by phenol phenolic varnish type, the cyanate ester resin that cresols phenolic varnish type polyatomic phenol obtains with reacting of halogen cyan, the cyanate ester resin obtaining with reacting of halogen cyan by the polynary aphthols of naphthols aralkyl-type etc.
Wherein, the flame retardant resistance of phenol phenolic varnish type cyanate ester resin and low heat expansion property are excellent, and the cross-linking density of 2,2 '-bis-(4-cyanate radical closes phenyl) isopropylidenes and dicyclopentadiene-type cyanate is controlled and moisture-proof reliability excellence.From the viewpoint of low heat expansion property, phenol phenolic varnish type cyanate ester resin particularly preferably.In addition, also can, further also with a kind or two or more other cyanate ester resin, be not particularly limited.
Aforementioned cyanate ester resin can be used separately.In addition, also two or more kinds may be used the different cyanate ester resin of weight-average molecular weight, or and with aforementioned cyanate ester resin and its prepolymer.
Generally, aforementioned prepolymer is by utilizing reacting by heating etc. by the aforementioned cyanate ester resin material that for example trimerizing obtains, and is formability in order to regulate resin combination, mobility and the material that preferably uses.
Aforementioned prepolymer is not particularly limited, when using that for example trimerization rate is the prepolymer of 20～50 % by weight, can shows good formability, mobility.
Content to aforementioned cyanate ester resin is not particularly limited, and the solids component benchmark in resin combination integral body, is preferably 5～60 % by weight, more preferably 10～50 % by weight.When the content of cyanate ester resin is in aforementioned range time, can more effectively improve thermotolerance and the flame retardant resistance of prepreg.When the content of cyanate ester resin is lower than aforementioned in limited time lower, the thermal expansivity of prepreg increases sometimes, thermotolerance reduces, when the content of cyanate ester resin surpasses aforementioned higher limit, and the strength decreased of prepreg sometimes.
Weight-average molecular weight to aforementioned cyanate ester resin is not particularly limited, and is preferably 5.0 * 10 2～4.5 * 10 3, be particularly preferably 6.0 * 10 2～3.0 * 10 3.When weight-average molecular weight is during lower than aforementioned lower value, the surface of prepreg produces viscosity sometimes, or physical strength reduces.In addition, when weight-average molecular weight surpasses aforementioned higher limit, the curing reaction of resin combination is accelerated sometimes, worsens with the adaptation of conductor layer.
In the present invention, the weight-average molecular weight of aforementioned cyanate ester resin can be measured with for example gel permeation chromatography (GPC), next specific with the weight molecular weight of polystyrene conversion.
Aforementioned resin is not particularly limited, by comprising bimaleimide resin, can improves thermotolerance.
As aforementioned bimaleimide resin, be not particularly limited, can enumerate: N, N '-(4,4 '-ditan) bismaleimides, two (3-ethyl-5-methyl-4-maleimide phenyl) methane, 2, the bimaleimide resins such as 2-two [4-(4-maleimide phenoxy group) phenyl] propane.Aforementioned bimaleimide resin also can, further also with a kind or two or more other bimaleimide resin, be not particularly limited.In addition, aforementioned bimaleimide resin can be used separately.In addition, also can be used together the bimaleimide resin that weight-average molecular weight is different, or also with aforementioned bimaleimide resin and its prepolymer.
Content to aforementioned bimaleimide resin is not particularly limited, and the solids component benchmark in resin combination integral body, is preferably 1～35 % by weight, is particularly preferably 5～20 % by weight.
(solidifying agent, curing catalyst)
The resin combination using in the present invention can be used together solidifying agent.As solidifying agent, be not particularly limited, for example, when using epoxy resin as aforementioned hot thermosetting resin, can be used as common the used phenol of solidifying agent of epoxy resin is solidifying agent, fatty amine, aromatic amine, Dyhard RU 100, dicarboxylic acid dihydrazide compound, acid anhydrides etc.
In addition, the resin combination using in the present invention can add curing catalyst as required.Aforementioned curing catalyst is not particularly limited, for example, can enumerates: organic metal salt, tertiary amines, imidazoles, organic acid, salt compound etc.As curing catalyst, both can use separately the derivative that comprises these materials at interior a kind, the derivative that also can comprise these materials is in interior two or more.
(coupling agent)
Aforementioned resin can also contain coupling agent.Coupling agent is in order to improve the interface wet ability of thermosetting resin and packing material and compounding.Thus, can make resin and packing material be fixed on equably on fiber weaving cloth, can improve the solder heat resistance after the thermotolerance of prepreg, especially moisture absorption.
Aforementioned coupling agent is not particularly limited, for example, can enumerates: epoxy silane coupling agent, cationic silane coupling agent, amino silicane coupling agent, titanic acid ester are coupling agent, silicone oil type coupling agent etc.Thus, the wettability with the interface of packing material can be improved, the thermotolerance of prepreg can be further improved thus.
Addition to aforementioned coupling agent is not particularly limited, and with respect to packing material 100 weight parts, is preferably 0.05～3 weight part, is particularly preferably 0.1～2 weight part.When content is during lower than aforementioned lower value, sometimes because improving stable on heating effect, reduces abundant coating packing material.In addition, when content surpasses aforementioned higher limit, sometimes reaction is brought to the reductions such as impact, flexural strength.
(other)
In addition, aforementioned resin can also be added the mentioned components such as flame retardant, ion capturing agent such as defoamer, flow agent, UV light absorber, whipping agent, antioxidant, fire retardant, phosphorus system, phosphonitrile additive in addition as required.
Prepreg of the present invention can obtain by the following method, that is, make fiber weaving cloth remain on the varnish that contains above-mentioned compositions of thermosetting resin in solvent, then, removes aforementioned solvents.Preparation method to aforementioned varnish is not particularly limited, preferred method is that for example, preparation is dispersed with the slurry of thermosetting resin and packing material in solvent, in this slurry, add the composition of other resin combination, and then add aforementioned solvents to make it dissolve mixing.Thus, can improve the dispersiveness of packing material, can make the silica dioxide granule of median size 5～100nm contained in aforementioned packing material be easy to enter fiber weaving cloth, can improve the impregnation of resin combination to fiber weaving cloth.
It should be noted that, in the present invention, in so-called solvent, contain compositions of thermosetting resin, resin that refers to solubility contained in aforementioned compositions of thermosetting resin etc. is dissolved in solvent, and insoluble packing material etc. are dispersed in solvent.
As aforementioned solvents, be not particularly limited, be preferably the solvent that aforementioned resin is demonstrated to good solubility, for example, can enumerate acetone, methyl ethyl ketone (MEK), pimelinketone (ANON), methyl iso-butyl ketone (MIBK) (MIBK), cyclopentanone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone etc.It should be noted that, in not bringing dysgenic scope, also can use poor solvent.
The solids component of the resin combination that aforementioned varnish is comprised (removing the composition after solvent from varnish) is not particularly limited, and is preferably 30～80 % by weight, is particularly preferably 40～70 % by weight.Thus, can improve the impregnation of resin combination to fiber weaving cloth.In addition, the surface smoothness in the time of can suppressing to be coated with, thickness deviation etc.
For making the weave cotton cloth method of the aforementioned varnish of impregnation of aforementioned fibers, for example can enumerate: the method that impregnation of fibers is weaved cotton cloth in varnish; The method of utilizing various coating machines to be coated with; The method spraying by injection; On base material, be coated with varnish and make it dry and make resin flake, the mode that this resin flake is contacted with fiber weaving cloth with resin layer configures and makes the method etc. of its crimping.In these methods, the method that preferably impregnation of fibers is weaved cotton cloth in varnish.Thus, can improve the impregnation of compositions of thermosetting resin to fiber weaving cloth.It should be noted that, when impregnation of fibers is weaved cotton cloth in varnish, can use common impregnation coating apparatus.In addition, the solvent by making aforementioned varnish, at for example at 90～180 ℃ dry 1～10 minute, can obtain the prepreg of semicure.
Aforementioned prepreg consists of following layer: the resin layer being formed by resin combination on the fiber weaving cloth layer being formed by fiber weaving cloth, the two sides that is formed at this fiber weaving cloth layer.Thickness to aforementioned fibers nonwoven fabric layer is not particularly limited, and is preferably 10～200 μ m, more preferably 10～140 μ m, 20～90 μ m more preferably.The thickness of aforementioned resin layer (the only thickness of one deck of one side) is not particularly limited, is preferably 0.5～20 μ m, be particularly preferably 2～10 μ m.By making the thickness of fiber weaving cloth layer and the thickness of resin layer, be in aforementioned range, better with adaptation and the surface smoothness of conductor layer.
Integral thickness to aforementioned prepreg is not particularly limited, and is preferably 30～220 μ m, is particularly preferably 40～165 μ m.Thus, the operability of prepreg is good, also can tackle slimming.
In aforementioned prepreg, form in the precursor of fiber weaving cloth, there is not the space with length more than 50 μ m in the direction of extending at the fiber that forms precursor.Thus, can improve the insulating reliability that insulation layer is used the printed circuit board (PCB) of prepreg.And then, in forming the precursor of fiber weaving cloth, more than the direction of preferably extending at the fiber that forms precursor does not exist and has 20 μ m, the space of length more than 10 μ m especially.
In addition, in aforementioned prepreg, the diameter in the precursor of formation fiber weaving cloth is that the number density in spaces more than 50 μ m is 50cm -3below.At this moment also can improve the insulating reliability that insulation layer is used the printed circuit board (PCB) of prepreg.And then the number density that preferably forms diameter in the precursor of fiber weaving cloth and be spaces more than 50 μ m is 20cm -3especially 10cm below, -3below.
It should be noted that, by the median size of silica dioxide granule that exists in suitable adjusting precursor, the volume densities of fiber weaving cloth etc. can realize length, the number density in the space in above-mentioned precursor.
2. veneer sheet
Next, veneer sheet is described.
Veneer sheet of the present invention is characterised in that, it solidifies aforementioned prepreg of the present invention and obtain.In addition, veneer sheet of the present invention preferably, aforementioned prepreg of the present invention at least one outside face be provided with conductor layer.
Aforementioned prepreg both can have been used 1, also can use 2 above laminations and the layered product that obtains.Being set, the veneer sheet that conductor layer forms (is sometimes referred to as below " metal-coated laminated board ".) situation under, can and carry out heating and pressurizing by laminated metal foil on above-mentioned prepreg and obtain.When using 1 prepreg, can descend two sides or one side overlapped metal paper tinsel thereon, when using the layered product that more than 2 prepreg lamination is obtained, can be at outermost upper and lower surface or the one side overlapped metal paper tinsel of this layered product.Then, the overlapping body that overlapping prepreg and tinsel are formed carries out heating and pressurizing moulding, can obtain metal-coated laminated board thus.
As aforementioned metal paper tinsel, for example, can enumerate copper, copper series alloy, aluminium, aluminum series alloy, silver, silver and be associated gold, gold, gold and be associated gold, zinc, Zn based alloy, nickel, nickel system alloy, tin, tin and be associated the tinsels such as gold, iron, iron-based alloy.In addition, also can form by plating the conductor layers such as copper as above, copper series alloy.
When manufacturing metal-coated laminated board, the temperature heating is not particularly limited, be preferably 120～220 ℃, be particularly preferably 150～200 ℃.The pressure pressurizeing is not particularly limited, is preferably 0.5～5MPa, be particularly preferably 1～3MPa.In addition, also can in high temperature groove etc., at the temperature of 150～300 ℃, carry out after fixing as required.
In addition, as the another kind of method of manufacturing metal-coated laminated board of the present invention, can enumerate the manufacture method of metal-coated laminated board of the tinsel of the use resin layer shown in Fig. 1.First, prepare to be coated with in tinsel 11 with coating machine the tinsel 10 of the resin layer of uniform resin layer 12.Then, in the both sides of fiber weaving cloth 20, the tinsel 10,10 of configuration resin layer also makes resin layer 12 for inner side (Fig. 1 (a)), heats in a vacuum under 60～130 ℃, the condition of pressurization 0.1～5MPa and makes its lamination impregnation.Thus, obtain (b) with prepreg 41(Fig. 1 of tinsel).Then, the prepreg 41 with tinsel is directly carried out to heating and pressurizing moulding, can obtain thus (c) of metal-coated laminated board 51(Fig. 1).
And then, as the another kind of method of manufacturing metal-coated laminated board of the present invention, also can enumerate the manufacture method of metal-coated laminated board of the polymeric membrane thin slice of the use resin layer shown in Fig. 2.First, prepare to be coated with on polymeric membrane thin slice 31 with coating machine the polymeric membrane thin slice 30 of the resin layer of uniform resin layer 32.Then, at the polymeric membrane thin slice 30,30 of the both sides configurations resin layer of fiber weaving cloth 20 and make resin layer 32 for inner side (Fig. 2 (a)), in a vacuum, make its lamination impregnation under the condition of 60～130 ℃ of heating, pressurization 0.1～5MPa.Thus, can obtain (b) with prepreg 42(Fig. 2 of polymeric membrane thin slice).Then, after the polymeric membrane thin slice 31 of at least one side of the prepreg with polymeric membrane thin slice 42 is peeled off (in (c) of Fig. 2 for peeling off two sides), at (d) that peeled off face configuration tinsel 11(Fig. 2 of polymeric membrane thin slice 31), carry out heating and pressurizing moulding.Thus, can obtain metal-coated laminated board 52(Fig. 2 (e)).And then, when peeling off the polymeric membrane thin slice on two sides, same with aforesaid prepreg, also can lamination more than 2.At lamination more than 2 during prepreg, outermost upper and lower surface or one side configuration tinsel or polymeric membrane thin slice at the prepreg of lamination, carry out heating and pressurizing moulding, can obtain metal-coated laminated board thus.The thickness and precision of the metal-coated laminated board obtaining by above-mentioned manufacture method is high, even thickness, and surface smoothness is excellent.And owing to can obtaining the metal-coated laminated board that shaping and deformation is little, therefore, use the warpage of printed circuit board (PCB) that the metal-coated laminated board obtain by this manufacture method makes and semiconductor device little, warpage deviation is also little.And then can yield rate manufacture well printed circuit board (PCB) and semiconductor device.
Condition as aforementioned heating and pressurizing moulding, is not particularly limited temperature, is preferably 120～250 ℃, is particularly preferably 150～220 ℃.The aforementioned pressure pressurizeing is not particularly limited, is preferably 0.1～5MPa, be particularly preferably 0.5～3MPa.And then also can in high temperature groove etc., at the temperature of 150～300 ℃, carry out after fixing as required.
Metal-coated laminated board to Fig. 1～2 grade is not particularly limited, and for example, can manufacture with the device of tinsel and the device of manufacture metal-coated laminated board of manufacturing resin layer.
In the device of tinsel of manufacturing aforementioned resin layer, tinsel such as can by use by rectangular sheet product make roll form tinsel etc., and send out continuously thus supply.By the feedway of resin, resinous varnish is supplied in tinsel continuously with specified amount.Here, as resinous varnish, can use resin combination of the present invention to dissolve, be dispersed in solvent and the coating fluid obtaining.The glue spread of resinous varnish can be by comma roller and this comma roller the gap of support roll control.Be coated with the tinsel of resinous varnish of specified amount in the delivered inside of the hot-air drying device of lateral transfer type, in fact the dry organic solvent that contains in resinous varnish etc. of removing, can form the tinsel that curing reaction proceeds to the resin layer in way as required.The tinsel of resin layer also can direct winfing, but utilizes laminating roll, is being formed with the folded protective membrane that stresses of resin layer, coiling lamination the tinsel of resin layer of this protective membrane, obtain the tinsel of the tape insulation resin layer of roll form.When using the manufacture method of Fig. 1～2 grade, compare with the manufacture method of impregnation varnish in the past, can control uniform amount of resin, in face, thickness and precision is excellent, and therefore, the warpage deviation of semiconductor device that is equipped with semiconductor element is little, and yield rate improves.
In addition, when obtaining metal-coated laminated board by above-mentioned manufacture method, need to consider the impregnation of resin combination to fiber weaving cloth.Packing material is by being used the silica dioxide granule of median size 5～100nm, especially the impregnation of fiber base material is improved, therefore, when heating and pressurizing moulding, the resin combination that can suppress in metal-coated laminated board flows, and can suppress the inhomogeneous movement of molten resin, therefore, the striated that can prevent metal-coated laminated board surface is uneven, and can form uniform thickness.
3. printed circuit board (PCB)
Next, printed circuit board (PCB) of the present invention is described.
Printed circuit board (PCB) of the present invention is that above-mentioned prepreg and/or above-mentioned veneer sheet are formed for internal layer circuit substrate.
Or printed circuit board (PCB) of the present invention is that above-mentioned prepreg is formed for the insulation layer on internal layer circuit.
It should be noted that, in the situation that internal layer circuit substrate uses the printed circuit board (PCB) of prepreg of the present invention or veneer sheet of the present invention, the layer that the prepreg in internal layer circuit substrate solidify to form is insulation layer.
In the present invention, printed circuit board (PCB) is that the printed circuit board (PCB) that the conductor layers such as tinsel form conductor circuit layer is set on insulation layer, can be any in single-clad board (laminate), two-face printing circuit card (two laminates) and multilayer printed circuit board (multi-ply wood).Multilayer printed circuit board be utilize plated-through-hole method (plated through-hole), lamination method etc. overlapping 3 layers of above printed circuit board (PCB), can and carry out heating and pressurizing moulding by lapped insulation layer on internal layer circuit substrate and obtain.As aforementioned internal layer circuit substrate, for example, can use the internal layer circuit substrate obtaining with veneer sheet of the present invention and/or prepreg of the present invention.As the internal layer circuit substrate obtaining with veneer sheet of the present invention, for example, can preferably use the internal layer circuit substrate forming by following operation: do not having on the veneer sheet of the present invention of tinsel, utilize the conductor circuit of the formation predetermined patterns such as semi-additive process, and this conductor circuit is partly carried out to Darkening process; In the tinsel of metal-coated laminated board of the present invention, form the conductor circuit of predetermined pattern, and this conductor circuit is partly carried out to Darkening process.
In addition, as the internal layer circuit substrate obtaining with prepreg of the present invention, can also use the internal layer circuit substrate forming by following operation: the electrical/electronic components such as mounting condenser, resistance, chip on the insulativity supporter being formed by cured resin etc., lamination prepreg of the present invention thereon, and carry out heat-pressure curing, on the parts built-in substrate obtaining thus, utilize the conductor circuit of the formation predetermined patterns such as semi-additive process, and this conductor circuit is partly carried out to Darkening process.
And then, in the present invention, also can by use the veneer sheet of the invention described above and/or internal layer circuit substrate that prepreg of the present invention obtains or on the conductor circuit of known internal layer circuit substrate in the past further lamination prepreg of the present invention, carry out heat-pressure curing and the circuit substrate that obtains is made as internal layer circuit substrate.As the insulation layer on aforementioned internal layer circuit, can use prepreg of the present invention.It should be noted that, when using prepreg of the present invention as insulation layer on aforementioned internal layer circuit, aforementioned internal layer circuit substrate can not be also the internal layer circuit substrate that uses prepreg of the present invention or veneer sheet to obtain.
Below, as the typical example of printed circuit board (PCB) of the present invention, to using the multilayer printed circuit board of metal-coated laminated board of the present invention as internal layer circuit substrate, while using prepreg of the present invention as insulation layer to describe.
By the one or two sides at aforementioned metal-coated laminated board, form the conductor circuit of predetermined pattern, and this conductor circuit is partly carried out to Darkening process, make internal layer circuit substrate.Formation method to aforementioned conductor circuit is not particularly limited, and can utilize the known methods such as subraction, additive process, semi-additive process to carry out.In addition, on internal layer circuit substrate, can utilize drilling machine processing, laser processing etc. to form through hole, by plating etc., realize the electrical connection on two sides.Because aforementioned internal layer circuit substrate comprises metal-coated laminated board of the present invention, therefore, especially by laser processing, can form the through hole of the precision excellence of aperture, shape etc.Aforementioned laser can be used excimer laser, UV laser and carbon dioxide laser etc.
Then, overlapping aforementioned prepreg carry out heating and pressurizing moulding on this internal layer circuit substrate, is further heating and curing, and forms thus insulation layer.Particularly, make aforementioned prepreg and aforementioned internal layer circuit substrate overlapping, with vacuum pressure type laminating machine device etc., carry out heating under vacuum extrusion forming, thereafter, with hot-air drying device etc., insulation layer is heating and curing.Here, the condition as carrying out heating and pressurizing moulding, is not particularly limited, and as an example wherein, can under the condition of 60～160 ℃ of temperature, pressure 0.2～3MPa, implement.In addition, as making its condition being heating and curing, be not particularly limited, as an example wherein, can under 140～240 ℃ of temperature, the condition of 30～120 minutes time, implement.
Then, the insulation layer irradiating laser to lamination, forms aperture portion (via).Aforementioned laser can be used with through hole and form the laser that middle used laser is identical.Because aforementioned dielectric layer comprises prepreg of the present invention, therefore, by laser processing, can form the aperture portion of the precision excellence of aperture, shape etc.
For gum residue after laser radiation (stain) etc., the processing that preferably utilizes oxygenants such as permanganate, dichromate etc. to remove, carries out decontamination processing.If decontamination is processed insufficient and can not fully be guaranteed soil release performance, even if aperture portion is carried out to metal deposition processing, also can worry because of the former of stain thereby can not fully guarantee top conductor circuit layer and the powered of lower floor's conductor circuit layer.In addition, by carrying out decontamination processing, can therefore, process by Metal plating when surface of insulating layer forms conductor layer simultaneously by the surface coarsening of level and smooth insulation layer, the adaptation of surface of insulating layer and conductor layer is excellent.It should be noted that, also can before forming aperture portion by laser radiation, at surface of insulating layer, form conductor layer.
Then, in aperture portion and surface of insulating layer, carry out Metal plating processing, form conductor layer.On aforementioned dielectric layer surface, further utilize aforesaid known method etc. to form conductor circuit.It should be noted that, by carrying out Metal plating in aperture portion, process to form conductor layer, can seek the conducting of top conductor circuit layer and lower floor's conductor circuit layer.
Further lamination insulation layer, with aforementioned same formation conductor circuit, in multilayer printed circuit board, after forming conductor circuit, forms soldering-resistance layer at outermost layer.Formation method to soldering-resistance layer is not particularly limited, and for example, can form by the following method: the solder resist of overlapping (lamination) dry-film type, the method for utilizing exposure and developing and form; Or to having printed the matter utilization exposure of aqueous resist and the method for developing and forming.The multilayer printed circuit board obtaining during for semiconductor device, for being installed, semiconductor element is being arranged to connecting electrode portion.Can be with the suitable coating connecting electrode of the metal tunicle portion of gold-plated, nickel plating and plating scolder etc.
4. semiconductor device
Next, semiconductor device of the present invention is described.
On the aforementioned printed circuit board (PCB) obtaining, the semiconductor element with solder projection is installed, by solder projection, realization is connected with aforementioned printed circuit board (PCB).Then, between printed circuit board (PCB) and semiconductor element, fill sealing resin, form semiconductor device.Preferred solder projection consists of the alloy that comprises tin, lead, silver, copper, bismuth etc.
Method of attachment for semiconductor element and printed circuit board (PCB), use flip-chip bonder etc. to carry out after the position alignment of solder projection of connecting electrode portion on printed circuit board (PCB) and semiconductor element, more than solder projection being heated to fusing point with IR reflow device, hot plate, other heating unit, printed circuit board (PCB) and solder projection melting are engaged, connect thus.It should be noted that, in order to make connection reliability good, the connecting electrode portion on printed circuit board (PCB) forms the layer of the metal that the fusing points such as soldering paste are lower in advance.Before this bonding process, also can improve connection reliability by the top layer coating solder flux of the connecting electrode portion on solder projection and/or printed circuit board (PCB).
Embodiment
Below, based on embodiment and comparative example, explain the present invention, but the present invention is not limited thereto.
The fiber weaving cloth using in embodiment and comparative example is by woven the weaving cotton cloth of glass fibre plain weave of JIS R3413 regulation, is the following glass fibre A～L that weaves cotton cloth.
A: use the glass fiber yarn of T glass, E1101/0, the filling density radical of every 25mm of organizine and tram is 44.5,42, and the thickness of opening after fine flat processing is 130 μ m, and mass area ratio is 155g/m 2
B: use the glass fiber yarn of E glass, DE1501/0, the filling density radical of every 25mm of organizine and tram is 46.5,44, and the thickness of opening after fine flat processing is 95 μ m, and mass area ratio is 121g/m 2
C: use the glass fiber yarn of T glass, E2251/0, the filling density radical of every 25mm of organizine and tram is 65,64, and the thickness of opening after fine flat processing is 95 μ m, and mass area ratio is 121g/m 2
D: use the glass fiber yarn of D glass, E2251/0, the filling density radical of every 25mm of organizine and tram is 65,64, and the thickness of opening after fine flat processing is 95 μ m, and mass area ratio is 121g/m 2
E: use the glass fiber yarn of T glass, D4501/0, the filling density radical of every 25mm of organizine and tram is 59,59, and the thickness of opening after fine flat processing is 46 μ m, and mass area ratio is 53g/m 2
F: use the glass fiber yarn of T glass, BC15001/0, the filling density radical of every 25mm of organizine and tram is 90,90, and the thickness of opening after fine flat processing is 20 μ m, and mass area ratio is 24g/m 2
G: use the glass fiber yarn of T glass, C12001/0, the filling density radical of every 25mm of organizine and tram is 74,77, and the thickness of opening after fine flat processing is 25 μ m, and mass area ratio is 31g/m 2
H: use the glass fiber yarn of T glass, E1101/0, the filling density radical of every 25mm of organizine and tram is 44.5,42, and the thickness of opening after fine flat processing is 115 μ m, and mass area ratio is 155g/m 2
I: use the glass fiber yarn of T glass, E1101/0, the filling density radical of every 25mm of organizine and tram is 43,40, and the thickness of opening after fine flat processing is 145 μ m, and mass area ratio is 150g/m 2
J: use the glass fiber yarn of T glass, E2251/0, the filling density radical of every 25mm of organizine and tram is 59,54, and the thickness of opening after fine flat processing is 97 μ m, and mass area ratio is 100g/m 2
K: use the glass fiber yarn of T glass, D4501/0, the filling density radical of every 25mm of organizine and tram is 60,47, and the thickness of opening after fine flat processing is 50 μ m, and mass area ratio is 48g/m 2
L: use the glass fiber yarn of T glass, C12001/0, the filling density radical of every 25mm of organizine and tram is 68,72, and the thickness of opening after fine flat processing is 27 μ m, and mass area ratio is 25g/m 2
The varnish using in embodiment and comparative example is to make to contain in solvent by following varnish Production Example 1～7 varnish that blended resin composition is manufactured.
(varnish Production Example 1)
Make to contain in methyl ethyl ketone blending epoxy (HP-5000 that DIC company manufactures) 6 weight parts, phenol phenolic varnish type cyanate ester resin (PT30 that LONZA company manufactures) 12 weight parts, phenol is solidifying agent (the bright MEH-7851-4L with changing into company's manufacture) 6 weight parts, silica dioxide granule (the NSS-5N that Tokuyama Corporation manufactures, median size 70nm) 10 weight parts, spherical silicon dioxide (Admatechs Co., Ltd. the SO-31R manufacturing, median size 1.0 μ m) 65 weight parts, epoxy silane (KBM-403E that chemical industrial company of SHIN-ETSU HANTOTAI manufactures) 1.0 weight parts, with high-speed stirring apparatus, stir, obtain composition epoxy resin and with solids component benchmark, count the varnish of 70 % by weight.It should be noted that, when containing packing material integral body contained in the resin combination of mixing in varnish and be made as 100 quality %, in this packing material, contained silica dioxide granule is that 13 quality %, spherical silicon dioxide are 87 quality %.
(varnish Production Example 2)
Make to contain in dimethyl formamide the biphenyl aralkyl-type epoxy resin of mixing as epoxy resin (NC-3000 that Japanese chemical drug company manufactures) 9 weight parts, bimaleimide resin (KI Chemical Industry Co., Ltd. the BMI-70 manufacturing) 17 weight parts, 4, 4 '-diaminodiphenyl-methane, 3 weight parts, silica dioxide granule (the NSS-5N that Tokuyama Corporation manufactures, median size 70nm) 10 weight parts, boehmite (the BMB that He He lime company manufactures, median size 0.5 μ m) 60 weight parts, epoxy silane (KBM-403E that chemical industrial company of SHIN-ETSU HANTOTAI manufactures) 1.0 weight parts.Then, with high-speed stirring apparatus, stir, so that the mode that nonvolatile component is 70 % by weight regulates, prepare resinous varnish.It should be noted that, when containing packing material integral body contained in the resin combination of mixing in varnish and be made as 100 quality %, in this packing material, contained silica dioxide granule is that 14 quality %, boehmite are 86 quality %.
(varnish Production Example 3)
Make to contain in methyl ethyl ketone and mix biphenyl aralkyl-type epoxy resin (NC-3000FH that Japanese chemical drug company manufactures) 20 weight parts, naphthalene type epoxy resin (HP4032D that DIC Corporation manufactures) 5 weight parts, cyanate ester resin (the derivative of the SN485 that Toto Kasei KK manufactures, naphthol type) 17 weight parts, bimaleimide resin (KI Chemical Industry Co., Ltd. the BMI-70 manufacturing) 7.5 weight parts, silica dioxide granule (the NSS-5N that Tokuyama Corporation manufactures, median size 70nm) 7 weight parts, spherical silicon dioxide (Admatechs Co., Ltd. the SO-31R manufacturing, median size 1.0 μ m) 35.5 weight parts, organic silicon granule (the KMP600 that Shin-Etsu Chemial Co., Ltd manufactures, median size 5 μ m) 7.5 weight parts, zinc octoate 0.01 weight part, epoxy silane (KBM-403E that chemical industrial company of SHIN-ETSU HANTOTAI manufactures) 0.5 weight part.Then, with high-speed stirring apparatus, stir, so that the mode that nonvolatile component is 70 % by weight regulates, prepare resinous varnish.It should be noted that, when containing packing material integral body contained in the resin combination of mixing in varnish and be made as 100 quality %, in this packing material, contained silica dioxide granule is that 14 quality %, spherical silicon dioxide are that 71 quality %, organic silicon granule are 15 quality %.
(varnish Production Example 4)
Make to contain in dimethyl formamide the biphenyl aralkyl-type epoxy resin of mixing as epoxy resin (NC-3000 that Japanese chemical drug company manufactures) 18.5 weight parts, bimaleimide resin (KI Chemical Industry Co., Ltd. the BMI-70 manufacturing) 34.9 weight parts, 4, 4 '-diaminodiphenyl-methane, 6.1 weight parts, silica dioxide granule (the NSS-5N that Tokuyama Corporation manufactures, median size 70nm) 5 weight parts, boehmite (the BMB that He He lime company manufactures, median size 0.5 μ m) 35 weight parts, epoxy silane (KBM-403E that chemical industrial company of SHIN-ETSU HANTOTAI manufactures) 0.5 weight part.Then, with high-speed stirring apparatus, stir, so that the mode that nonvolatile component is 70 % by weight regulates, prepare resinous varnish.It should be noted that, when containing packing material integral body contained in the resin combination of mixing in varnish and be made as 100 quality %, in this packing material, contained silica dioxide granule is that 12.5 quality %, boehmite are 87.5 quality %.
(varnish Production Example 5)
Make to contain in dimethyl formamide the biphenyl aralkyl-type epoxy resin of mixing as epoxy resin (NC-3000 that Japanese chemical drug company manufactures) 2.80 weight parts, bimaleimide resin (KI Chemical Industry Co., Ltd. the BMI-70 manufacturing) 5.27 weight parts, 4, 4 '-diaminodiphenyl-methane, 0.93 weight part, silica dioxide granule (the NSS-5N that Tokuyama Corporation manufactures, median size 70nm) 10 weight parts, boehmite (the BMB that He He lime company manufactures, median size 0.5 μ m) 80 weight parts, epoxy silane (KBM-403E that chemical industrial company of SHIN-ETSU HANTOTAI manufactures) 1.0 weight parts.Then, with high-speed stirring apparatus, stir, so that the mode that nonvolatile component is 70 % by weight regulates, prepare resinous varnish.It should be noted that, when containing packing material integral body contained in the resin combination of mixing in varnish and be made as 100 quality %, in this packing material, contained silica dioxide granule is that 11 quality %, boehmite are 89 quality %.
(varnish Production Example 6)
Make to contain in methyl ethyl ketone blending epoxy (HP-5000 that DIC Corporation manufactures) 6 weight parts, phenol phenolic varnish type cyanate ester resin (PT30 that LONZA company manufactures) 12 weight parts, phenol is solidifying agent (the bright MEH-7851-4L with changing into company's manufacture) 6 weight parts, silica dioxide granule (the NSS-5N that Tokuyama Corporation manufactures, median size 70nm) 30 weight parts, spherical silicon dioxide (Admatechs Co., Ltd. the SO-31R manufacturing, median size 1.0 μ m) 45 weight parts, epoxy silane (KBM-403E that chemical industrial company of SHIN-ETSU HANTOTAI manufactures) 1.0 weight parts, with high-speed stirring apparatus, stir, obtain composition epoxy resin and with solids component benchmark, count the varnish of 70 % by weight.It should be noted that, when containing packing material integral body contained in the resin combination of mixing in varnish and be made as 100 quality %, in this packing material, contained silica dioxide granule is that 40 quality %, spherical silicon dioxide are 60 quality %.
(varnish Production Example 7)
Make to contain in methyl ethyl ketone blending epoxy (NC-3000 that Japanese chemical drug company manufactures) 6 weight parts, phenol phenolic varnish type cyanate ester resin (PT30 that LONZA company manufactures) 12 weight parts, phenol is solidifying agent (the bright MEH-7851-4L with changing into company's manufacture) 6 weight parts, spherical silicon dioxide (Admatechs Co., Ltd. the SO-31R manufacturing, median size 1.0 μ m) 75 weight parts, epoxy silane (KBM-403E that chemical industrial company of SHIN-ETSU HANTOTAI manufactures) 1.0 weight parts, with high-speed stirring apparatus, stir, obtain composition epoxy resin and with solids component benchmark, count the varnish of 70 % by weight.It should be noted that, when containing packing material integral body contained in the resin combination of mixing in varnish and be made as 100 quality %, in this packing material, contained silica dioxide granule is that 0 quality %, spherical silicon dioxide are 100 quality %.
The composition of the resin combination using in varnish Production Example 1～7 is shown in to table 1.It should be noted that, the compounding amount of each composition represents with weight part.
[table 1]
Use above-mentioned glass fibre to weave cotton cloth and above-mentioned varnish, make prepreg, metal-coated laminated board, printed circuit board (PCB) (internal layer circuit substrate), multilayer printed circuit board and semiconductor device.
< embodiment 1 >
(1) making of prepreg
The polyethylene terephthalate base material (hereinafter referred to as PET base material) that the varnish curtain coating being obtained by Production Example 1 is coated on to thickness 38 μ m is upper, makes solvent evaporates dry, so that the thickness of resin layer is 30 μ m under 140 ℃ of temperature, the condition of 10 minutes time.By the base material of aforementioned resin layer be configured in glass woven fabric A two sides so that resin layer contact with glass woven fabric, under pressure 0.5MPa, the temperature condition of 140 ℃, 1 minute, utilize vacuum pressure type laminating machine (MLVP-500 that Co., Ltd. Mingji Koito manufactures) to carry out heating and pressurizing, make resin combination impregnation.Thus, must arrive the prepreg (resin layer (one side): 10 μ m, fiber weaving cloth layer: 130 μ m) that two sides has the thickness 150 μ m of PET base material.
(2) making of metal-coated laminated board
The Copper Foil of 2 μ m of the two sides of aforementioned prepreg overlap zone carrier (mining company of Mitsui Metal Co., Ltd. manufactures, Micro Thin MT18Ex-2), under the condition of 220 ℃ of pressure 3MPa, temperature, heating and pressurizing moulding is 2 hours.Thus, obtain the metal-coated laminated board that two sides that prepreg solidifies the insulation layer of the thickness 150 μ m form has Copper Foil.
(3) making of prepreg for multilayer printed circuit board insulation layer
Make glass woven fabric (E glass woven fabric, E02Z, mass area ratio 17.5g/m that thickness 16 μ m, UNITIKA LTD. manufacture 2) varnish that obtains of the aforementioned Production Example 1 of impregnation, with dry 2 minutes of the process furnace of 180 ℃, the resin combination obtaining in prepreg was counted the prepreg (thickness 40 μ m) of approximately 78 % by weight with solids component benchmark.It should be noted that, the volume density of aforementioned glass woven fabric is 1.09g/cm 3, Gas permeability is 41cc/cm 2/ sec, flat ratio (thickness: width) be 1:16.In addition, the glass fibre that aforementioned glass woven fabric is 93GPa by making Young's modulus when tabular, to make tensile strength when tabular be 48GPa, the tensile strength of the length direction while making fiber weaving cloth is 90N/25mm forms.
(4) manufacture of printed circuit board (PCB) (internal layer circuit substrate)
From aforementioned metal-coated laminated board, peel off foils, with carbon dioxide laser (Mitsubishi Electric Corporation's manufacture, ML605GTX3-5100U2), in aperture under the condition of beam diameter approximately 120 μ m, energy 7～9mJ, irradiation number (number of shots) 6, form communicating pores.Then, this metal-coated laminated board is flooded 5 minutes in the swelling solution (Atotech Japan K.K. manufacture, Swelling Dip Securiganth P) of 70 ℃, and then flood 10 minutes in the potassium permanganate solution of 80 ℃ (Atotech Japan K.K. manufactures, Concentrate Compact CP), then neutralize and carry out roughening treatment.Then, by electroless plating (manufacture of upper village industrial, Thru-cup PEA process), realize the conducting between upper and lower Copper Foil.
Then,, on the surface of this chemical plating, utilize hot-roll lamination machine to paste the UV-radiation-sensitive dry film of thickness 25 μ m (Asahi Kasei Corporation's manufacture, San Fort UFG-255).Then, aim at the position of describing the glass mask that minimum feature/spacing is the pattern of 20/20 μ m (TOPIK CO., LTD manufactures).Then, use this glass mask, after exposing with exposure apparatus (EV-0800 that little Ye Ce device company manufactures), with aqueous sodium carbonate, develop, form Etching mask.Then, take chemical plating as power supply layer electrode, with 3A/dm 2carry out copper electroplating (81-HL that Ao Ye drugmaker manufactures) 25 minutes.Thus, form the pattern of the copper wiring of thickness approximately 20 μ m.Then, use stripping machine, utilize monoethanolamine solution (MITSUBISHI GAS CHEMCAL COMPANY, the R-100 that INC. manufactures), peel off aforementioned Etching mask.Then, utilize fast-etching (SAC-702M that Ren Yuan electricity Chan company manufactures and the pure water solution of SAC-701R35) to remove as useless Copper Foil and chemical plating beyond the pattern form to electricity layer, form the pattern of L/S=20/20 μ m.
Then, carry out the roughening treatment (MEC CO., LTD. manufacture, MEC etch BOND CZ-8100) of conductor circuit.By 35 ℃ of liquid temperatures, spray to press under the condition of 0.15MP and carry out spraying processing, what roughness 3 μ m left and right were implemented in copper surface roughenedly carries out this roughening treatment.Then, carry out the surface treatment (MEC CO., LTD. manufacture, MEC etch BOND CL-8300) of conductor circuit.In this surface treatment, under 25 ℃ of liquid temperatures, the dipping time condition of 20 seconds, flood, antirust processing is carried out in copper surface.Make thus printed circuit board (PCB) (internal layer circuit substrate).
(5) manufacture of multilayer printed circuit board
Then, take the aforementioned printed circuit board (PCB) obtaining as internal layer circuit substrate, at the aforementioned multilayer printed circuit board insulation layer of its two sides overlay configuration with prepreg with the Copper Foil of 2 μ m of carrier (mining company of Mitsui Metal Co., Ltd. manufactures, Micro Thin MT18Ex-2), with lamination vacuum lamination apparatus, carry out lamination, under 200 ℃ of temperature, pressure 3MPa, the condition of 120 minutes time, be heating and curing, obtain multilayer laminated body.Then, similarly carry out outer circuit formation with the manufacture method of aforementioned (4) printed circuit board (PCB) (internal layer circuit substrate), last, at circuit surface, form solder resist (TAIYO INK MFG, CO., LTD. manufacture, PSR4000/AUS308), obtain multilayer printed circuit board.
For aforementioned multilayer printed circuit board, the enforcement ENEPIG of the connecting electrode portion processing that solder projection is arranged that is equivalent to semiconductor element.By [1] clean, [2] soft etch processes, [3] cleanup acid treatment, [4] pre-preg, [5], give the operation of palladium catalyst, the processing of [6] electroless nickel plating, the processing of [7] electroless plating palladium, the processing of [8] electroless gold plating and carry out ENEPIG processing.
(6) manufacture of semiconductor device
Semiconductor device can obtain by the following method,, having implemented, on the printed circuit board (PCB) of ENEPIG processing, to utilize face-down bonding apparatus, by adding thermo-compressed, carry the semiconductor element (TEG chip, size 10mm * 10mm, thickness 0.1mm) with solder projection, then, with IR reflow stove, solder projection melting is engaged, then, fill aqueous sealing resin (SUMITOMO BAKELITE CO., LTD. manufacture, CRP-4152S), and aqueous sealing resin is solidified.It should be noted that, under 150 ℃ of temperature, the condition of 120 minutes, make aqueous sealing resin solidify.It should be noted that the solder projection that the eutectic that the solder projection use of aforesaid semiconductor element is comprised of Sn/Pb forms.Finally, with router monolithic, turn to the size of 14mm * 14mm, obtain semiconductor device.
< embodiment 2～3 and comparative example 1～6 >
The varnish that fiber weaving cloth shown in use table 4 and the Production Example by varnish obtain, the two sides that obtains similarly to Example 1 the insulation layer of prepreg, thickness 150 μ m has the metal-coated laminated board of Copper Foil, printed circuit board (PCB) (internal layer circuit substrate), multilayer printed circuit board and semiconductor device.
< embodiment 4～6 and comparative example 7 >
When making prepreg, the thickness of resin layer of the base material of resin layer is recorded as table 5, in addition, the varnish that fiber weaving cloth shown in use table 5 and the Production Example by varnish obtain, operation similarly to Example 1, the two sides that obtains the insulation layer of prepreg, thickness 100 μ m has the metal-coated laminated board of Copper Foil, printed circuit board (PCB) (internal layer circuit substrate), multilayer printed circuit board and semiconductor device.
It should be noted that, for the communicating pores formation of printed circuit board (PCB), use carbon dioxide laser (Mitsubishi Electric Corporation's manufacture, ML605GTX3-5100U2), in aperture beam diameter approximately 110 μ m, energy 7～9mJ, several 6 the condition of irradiating get off to carry out, and form the communicating pores of diameter 100 μ m.
< embodiment 7,8 and comparative example 8 >
For embodiment 7 and comparative example 8, when making prepreg, the thickness of resin layer of the base material of resin layer is recorded as table 6, in addition, the varnish that fiber weaving cloth shown in use table 6 and the Production Example by varnish obtain, the two sides that obtains similarly to Example 1 the insulation layer of prepreg, thickness 60 μ m has the metal-coated laminated board of Copper Foil, printed circuit board (PCB) (internal layer circuit substrate), multilayer printed circuit board and semiconductor device.
For embodiment 8, when making prepreg, the thickness of resin layer of the base material of resin layer is recorded as table 6, in addition, the varnish that fiber weaving cloth shown in use table 6 and the Production Example by varnish obtain, obtains similarly to Example 1 prepreg (integral thickness 30 μ m), the prepreg lamination of 2 these 30 μ m the two sides of solidifying the insulation layer of the thickness 60 μ m that form is had to metal-coated laminated board, internal layer circuit substrate, multilayer printed circuit board and the semiconductor device of Copper Foil.
It should be noted that, for the communicating pores formation of printed circuit board (PCB), use carbon dioxide laser (Mitsubishi Electric Corporation's manufacture, ML605GTX3-5100U2), in aperture beam diameter approximately 110 μ m, energy 6～8mJ, several 6 the condition of irradiating get off to carry out, and form the communicating pores of diameter 100 μ m.
< embodiment 9 and comparative example 9 >
When making prepreg, the thickness of resin layer of the base material of resin layer is recorded as table 7, in addition, the varnish that fiber weaving cloth shown in use table 7 and the Production Example by varnish obtain, the two sides that obtains similarly to Example 1 the insulation layer of prepreg, thickness 40 μ m has the metal-coated laminated board of Copper Foil, printed circuit board (PCB) (internal layer circuit substrate), multilayer printed circuit board and semiconductor device.
It should be noted that, for the communicating pores formation of printed circuit board (PCB), use carbon dioxide laser (Mitsubishi Electric Corporation's manufacture, ML605GTX3-5100U2), in aperture beam diameter approximately 110 μ m, energy 6～8mJ, several 6 the condition of irradiating get off to carry out, and form the communicating pores of diameter 100 μ m.
The prepreg, metal-coated laminated board, printed circuit board (PCB) (internal layer circuit substrate) and the semiconductor device that for embodiment and comparative example, obtain, carry out following evaluation.Assessment item is illustrated together with content.The evaluation result obtaining is shown in to table 4～7.
It should be noted that, because the measurement result of PKG warpage described later depends on the thickness of the insulation layer of metal-coated laminated board, therefore, by the thickness of the insulation layer of metal-coated laminated board, be that 150 embodiment of μ m and the evaluation result of comparative example are shown in table 4, by the thickness of the insulation layer of metal-coated laminated board, be that 100 embodiment of μ m and the evaluation result of comparative example are shown in table 5, by the thickness of the insulation layer of metal-coated laminated board, be that 60 embodiment of μ m and the evaluation result of comparative example are shown in table 6, by the thickness of the insulation layer of metal-coated laminated board, be that 40 embodiment of μ m and the evaluation result of comparative example are shown in table 7.
In addition, in table 4～7, packing material amount when the packing material amount (quality %) in resin combination represents resin combination integral body to be made as 100 quality %, the ratio of each composition when composition of packing material (quality) % represents packing material integral body to be made as 100 quality %.
< evaluation method >
(1) impregnation of resin combination
The prepreg that previous embodiment and comparative example are obtained solidifies after 1 hour at the temperature of 170 ℃, utilizes SEM(scanning electron microscope) observe section (for the scope of the 300mm of section portion of width), evaluating fibrous inside has tight.On image, the point of the white particulate of fibre profile is regarded as space.
Each symbol is as described below.
Zero: resin combination is impregnation well all, fibrous inside does not have the situation in space
*: fibrous inside has the situation in space
(2) formability
After the whole facet etch of Copper Foil of the metal-coated laminated board that previous embodiment and comparative example are obtained, utilize SEM(scanning electron microscope) scope of observing 500mm * 500mm, there is tight on the surface of evaluating insulation layer (being positioned at the surperficial resin layer of fiber weaving cloth layer).On image, the point of white particulate be regarded as space.
Each symbol is as described below.
Zero: there is no space
*: there is space
(3) moisture absorption solder heat resistance
The metal-coated laminated board that use obtains previous embodiment and comparative example cuts into the square and sample that obtains of 50mm * 50mm, based on JIS C-6481, the whole Copper Foils beyond half of one side of aforementioned sample are removed in etching, with pressure cooker testing machine (ESPEC CORP manufacture), under 121 ℃, 2 atmospheric conditions, process after 2 hours, in the solder bath of 260 ℃, flood 30 seconds, visual observations appearance change has or not extremely.
Each symbol is as described below.
Zero: there is no abnormal situation
*: there is swelling, peel off
(4) coefficient of linear thermal expansion (CTE) (ppm/K)
For coefficient of linear thermal expansion (CTE), use TMA(thermo-mechanical analysis) device (manufacture of TA Instruments company, Q400), make the test film of 4mm * 20mm, under the condition of 30～300 ℃ of temperature ranges, 10 ℃/min, load 5g, measures the CTE of 50～100 ℃ circulating for the 2nd time.It should be noted that, sample is used the sample after the Copper Foil etching of the metal-coated laminated board that each embodiment and comparative example are obtained is removed.
(5) laser processing
The printed circuit board (PCB) (internal layer circuit substrate) that uses previous embodiment and comparative example to obtain, measures the intersection overhang (cross protrusions) of the communicating pores after carbon dioxide laser processing, the circularity in aperture.Mensuration for intersection overhang and circularity, use colored 3D laser microscope (KEYENCE CORPORATION manufactures, installs name VK-9710), directly over the hole of laser light incident side, observe, mensuration is from the outstanding length of wall surface of the hole, intersect thus the mensuration of overhang, directly over the hole of laser light incident side, observe, measure major diameter and the minor axis of hole top diameter, calculate major diameter ÷ minor axis, carry out thus the mensuration of circularity.It should be noted that, the printed circuit board (PCB) (internal layer circuit substrate) that sample is used previous embodiment and comparative example to obtain, under the carbon dioxide laser condition shown in following table 2, from directly over observe diameter 100 μ m substrate just having finished of hole processing, get the mean value of 10 communicating poress.
[table 2]
Each symbol is as described below.
Zero: the overhang of intersecting is that to take interior and circularity be more than 0.85 situation to 10 μ m
△: the overhang of intersecting is the above or circularity of 10 μ m lower than 0.85 situation
*: the overhang of intersecting is the above and circularity of 10 μ m lower than 0.85 situation
(6) insulating reliability of communicating pores
The printed circuit board (PCB) (internal layer circuit substrate) that uses previous embodiment and comparative example to obtain, evaluates the insulating reliability between communicating pores.
0.1mm part between the through-hole wall of use printed circuit board (PCB), evaluates by METHOD FOR CONTINUOUS DETERMINATION under the condition applying voltage 10V, 130 ℃ of temperature, humidity 85%.It should be noted that, use height accelerated life test device (EHS-211(M that ESPEC CORP manufactures), AMI ion migration test macro) measure, at insulating resistance value, become lower than 10 8the moment of Ω finishes.
Each symbol is as described below.
◎: over 200 hours.
Zero: be 100 hours above and be below 200 hours.
△: be more than 50 hours and lower than 100 hours.
*: lower than 50 hours.
(7) PKG warpage
The semiconductor device (14mm * 14mm) that embodiment and comparative example are obtained is arranged on variable temperatures 3-d laser measurement instrument (Hitachi Technologies and Services, Ltd. manufacture, model LS220-MT100MT50) sample chamber in and make under semiconductor element face is, use said determination machine, measure the warpage of semiconductor device at room temperature (25 ℃) and 260 ℃.For the mensuration of warpage, measure the displacement of short transverse, the maximum value of displacement difference is made as to amount of warpage.It should be noted that, measurement range is size 13mm * 13mm.
Each symbol is as described in following table 3.It should be noted that, the mensuration of PKG warpage depends on the thickness of the insulation layer of metal-coated laminated board, and therefore, the thickness to the insulation layer of each metal-coated laminated board, as shown in table 3ly judges.
[table 3]
[table 4]
[table 5]
[table 6]
[table 7]
As the typical example of the observations of the impregnation of aforementioned (1) resin combination, the photo of the sectional view of the prepreg that embodiment 1 is obtained is shown in Fig. 3, and the photo of the sectional view of the prepreg that comparative example 4 is obtained is shown in Fig. 4.
As shown in Figure 4, because the impregnation of the resin combination of comparative example 4 is poor, therefore, in fiber weaving cloth, can be observed space.On the other hand, as shown in Figure 3, because the impregnation of the resin combination of embodiment 1 is good, therefore, in fiber weaving cloth, there is no space.
In embodiment 1, can think by the silica dioxide granule of nano-scale is entered in precursor, the impregnation of resin combination improves.With respect to this, in comparative example 4, owing to not containing the silica dioxide granule of nano-scale, therefore, can not seek the raising of the impregnation of resin combination.
Typical example as the formability observations of aforementioned (2) metal-coated laminated board, the whole facet etch of Copper Foil of the metal-coated laminated board that embodiment 1 is obtained surperficial photo be shown in Fig. 5, the whole facet etch of Copper Foil of the metal-coated laminated board that comparative example 6 is obtained surperficial photo be shown in Fig. 6, and then the SEM photo of the enlarged view of the space of observing in Fig. 6 (point of the white particulate on image) is shown in to Fig. 7, the SEM photo of the enlarged view of the section in the space of observing in Fig. 7 is shown in to Fig. 8.From Fig. 6,7,8, in comparative example 6, by the whole facet etch of metal-coated laminated board surface can be observed space.On the other hand, as shown in Figure 5, in embodiment 1, whole facet etch surface there is no space.
Fig. 9～12 mean the SEM photo of sectional view of a part of precursor of the fiber weaving cloth that forms the prepreg that embodiment 1 obtains.Fig. 9 represents the section parallel with the bearing of trend of precursor.Figure 10～12 represent the section vertical with the bearing of trend of precursor.
Known as shown in Fig. 9～12, in the prepreg obtaining at embodiment 1, in precursor, there is silica dioxide granule.
In the embodiment 1～9 shown in table 4～7, can obtain good prepreg impregnation.In addition, for other various characteristics, knownly also all can obtain good result.Think that this is owing to carrying out the making of prepreg under the condition entering at silica dioxide granule in the precursor that forms fiber weaving cloth.
It should be noted that, as controlling silica dioxide granule, enter the factor in precursor, can enumerate such as: the content of the median size of silica dioxide granule, the silica dioxide granule in packing material, the content of packing material in resin combination are, the multiple factors such as volume density of fiber weaving cloth.
From table 4～7, in embodiment 1～9, the packing material that in varnish, contained resin combination contains 50～85 quality % that account for this resin combination integral body, the silica dioxide granule that contains median size 5～100nm of 1～20 quality % in this packing material, and the volume density of fiber weaving cloth is 1.05～1.30g/cm 3.At this moment, the evaluation result of above-mentioned all assessment items is excellent.; for the prepreg of the present embodiment; known resin combination is excellent to the impregnation of fiber weaving cloth; for low heat expansion property; during as the insulation layer of printed circuit board (PCB), laser processing is excellent; the aperture in the hole forming by laser and the precision of shape are good, and can form and can suppress the outstanding hole of fiber.And then, for the prepreg of the present embodiment, can say because moisture absorption solder heat resistance is excellent, be therefore high heat resistance, because formability is excellent, so surface smoothness is also excellent, and then excellent with the adaptation of conductor layer.In addition, because the PKG warpage of semiconductor device of the present invention is little, therefore, the prepreg of known the present embodiment is low heat expansion property, and is high rigidity.
Comparative example 1 also can obtain good prepreg impregnation.
Yet in comparative example 1, CTE and package warpage can not obtain good result.Therefore think that this is that resinous principle due to the low only resin combination of content of packing material enters and suppressed silica dioxide granule in precursor and enter in precursor.Thus, think, can not highly-filled packing material, the CTE of prepreg raises, and has produced package warpage.
In addition, in comparative example 6, can not obtain good result.Think that this is owing to can not making the resin combination impregnation of q.s because volume density is low, therefore also suppressed contained silica dioxide granule in resin combination and entered in precursor.In addition, because the volume density because of fiber weaving cloth is little, become thicker fiber base material, therefore, the thickness attenuation of the resin layer on the top layer of prepreg.Therefore, think that formability, moisture absorption solder heat resistance are poor, although CTE has well produced PKG warpage.
In comparative example 4 and 7～9, for the impregnation of prepreg, can not obtain good result.In comparative example 4 and 7～9, in the resin combination of formation prepreg, do not contain the silica dioxide granule of nano-scale.Therefore, think that silica dioxide granule does not enter in precursor, can not seek the raising of the impregnation of resin combination.Thus, other various characteristics such as CTE and package warpage can not obtain good result.
In comparative example 7, because the volume density of fiber weaving cloth is little therefore laser processing is poor, because of impregnation poor therefore the insulating reliability of communicating pores is poor.In addition, because having used thicker fiber weaving cloth, therefore the thickness attenuation of the resin layer of prepreg, formability, moisture absorption solder heat resistance are poor, have produced PKG warpage.
In comparative example 8 and 9, because the thickness of insulating layer of metal-coated laminated board is thinner, therefore, the insulating reliability of formability, moisture absorption solder heat resistance, communicating pores is excellent.Yet because the volume density of fiber weaving cloth is little, so laser processing can not obtain good result.
In comparative example 2,3 and 5, for the impregnation of prepreg, can not obtain good result.In addition, for other various characteristics, can not obtain good result.In comparative example 2, think due to the too high levels of packing material, therefore, can not obtain the mobility of the silica dioxide granule in resin combination, result has suppressed silica dioxide granule and has entered in precursor.In comparative example 3, think that therefore, cohesion has occurred the silica dioxide granule of nano-scale because the content of the silica dioxide granule of nano-scale is high, result has suppressed silica dioxide granule and has entered in precursor.In comparative example 5, think because the volume density of fiber weaving cloth is large, therefore, suppressed silica dioxide granule and entered in precursor.
In comparative example 5, because the volume density of fiber weaving cloth is excessive, therefore, the impregnation of resin combination is poor, and moisture absorption solder heat resistance is poor, the insulating reliability inequality of laser processing and communicating pores.
In comparative example 6, because the volume density of fiber weaving cloth is little, therefore, the insulating reliability of laser processing and communicating pores is poor.And then, because the volume density because of fiber weaving cloth is little, become thicker fiber base material, therefore, the thickness attenuation of the resin layer on the top layer of prepreg.Therefore, formability, moisture absorption solder heat resistance are poor, have produced PKG warpage.
It is basic right of priority No. 2011-012166 that the application has required take the Japanese publication Patent of submitting on January 24th, 2011, and its content is all introduced in the application.

Claims (13)

1. a prepreg, it is the prepreg that the fiber weaving cloth impregnation resin combination that makes to consist of precursor forms,
The volume density of described fiber weaving cloth is 1.05～1.30g/cm 3,
Described resin combination at least comprises thermosetting resin and packing material,
The ratio that the solids component of take with respect to described resin combination is 50～85 quality % contains described packing material, and the ratio that to take with respect to described packing material be 1～20 quality % contains the silica dioxide granule that median size is 5～100nm,
In described precursor, there is described silica dioxide granule.
2., wherein, in described precursor, there is not the space with length more than 50 μ m in the direction that forms the fiber extension of described precursor in prepreg according to claim 1.
3. prepreg according to claim 1, wherein, its integral thickness is 30～220 μ m.
4. prepreg according to claim 1, wherein, described precursor consists of glass fibre, and described glass fibre at least contains SiO with the ratio of 50～100 quality % 2, with the ratio of 0～30 quality %, contain Al 2o 3, with the ratio of 0～30 quality %, contain CaO.
5. prepreg according to claim 4, wherein, described glass fibre is used at least one glass selecting in the group that free T glass, D glass, E glass, NE glass, silica glass form to form.
6. prepreg according to claim 4, wherein, to make Young's modulus when tabular be 50～100GPa to described glass fibre, make tensile strength when tabular is that 25GPa tensile strength above, the length direction while making fiber weaving cloth is more than 30N/25mm.
7. prepreg according to claim 4, wherein, the Gas permeability of described fiber weaving cloth is 1～80cc/cm 2/ sec.
8. prepreg according to claim 1, wherein, utilizes containing silicane or the alkyl silazane class of functional group described silica dioxide granule has been implemented to surface treatment.
9. a veneer sheet, it solidifies prepreg claimed in claim 1 and obtain.
10. veneer sheet according to claim 9, wherein, the face at least one outside of described prepreg is provided with conductor layer.
11. 1 kinds of printed circuit board (PCB)s, it forms prepreg claimed in claim 1 or veneer sheet claimed in claim 9 for internal layer circuit substrate.
12. printed circuit board (PCB)s according to claim 11, wherein, prepreg claimed in claim 1 is arranged on described internal layer circuit substrate as insulation layer.
13. 1 kinds of semiconductor devices, it is that semiconductor element mounted thereon forms on the printed circuit board (PCB) described in claim 11.
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