CN203093220U - Laminate, laminated board, multilayer laminated board and printed wiring board - Google Patents

Laminate, laminated board, multilayer laminated board and printed wiring board Download PDF

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Publication number
CN203093220U
CN203093220U CN2012204885689U CN201220488568U CN203093220U CN 203093220 U CN203093220 U CN 203093220U CN 2012204885689 U CN2012204885689 U CN 2012204885689U CN 201220488568 U CN201220488568 U CN 201220488568U CN 203093220 U CN203093220 U CN 203093220U
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China
Prior art keywords
layer
plywood
glass
duplexer
resin
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Expired - Lifetime
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CN2012204885689U
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Chinese (zh)
Inventor
青岛真裕
高桥佳弘
山崎由香
上方康雄
村井曜
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Showa Denko Materials Co Ltd
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Hitachi Chemical Co Ltd
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    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10614—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer comprising particles for purposes other than dyeing
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10697—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer being cross-linked
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H01L23/145—Organic substrates, e.g. plastic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H01L23/15—Ceramic or glass substrates
    • 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
    • H05K1/0271—Arrangements for reducing stress or warp in rigid printed circuit boards, e.g. caused by loads, vibrations or differences in thermal expansion
    • 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
    • H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
    • 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
    • H05K1/036—Multilayers with layers of different types
    • 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
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • 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
    • H05K1/18—Printed circuits structurally associated with non-printed electric components
    • H05K1/189—Printed circuits structurally associated with non-printed electric components characterised by the use of a flexible or folded printed circuit
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • 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
    • 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
    • H05K2201/01—Dielectrics
    • H05K2201/0183—Dielectric layers
    • H05K2201/0191—Dielectric layers wherein the thickness of the dielectric plays an important role
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)

Abstract

The utility model relates to a laminate which comprises more than one fibrous resin composition layer and more than one glass substrate layer, wherein the fibrous resin composition layer is made from thermosetting resin where a fiber base material is dispersed, and the glass substrate layer accounts for 10-70% of the volume of the whole laminate. The utility model relates to a laminated board which comprises more than one fibrous resin condensate layer and more than one glass substrate layer, wherein the fibrous resin condensate layer is made from thermosetting resin condensate where a fiber base material is dispersed, and the glass substrate layer accounts for 10-70% of the volume of the whole laminated board. The utility model relates to a printed wiring board which is provided with the laminated board and wires arranged on the surface of the laminated board.

Description

Duplexer, plywood, multilayer laminate and printing distributing board
Technical field
The utility model relates to and is suitable for duplexer and the plywood that semiconductor-sealing-purpose or printing distributing board are used, and has used printing distributing board, multilayer laminate, and the manufacture method of plywood of this plywood.
Background technology
In recent years, the slimming of e-machine, light-weighted requirement are strengthened day by day, slimming, the densification of semiconductor packages, printing distributing board constantly develop.For corresponding with these slimmings, densification, electronic unit stably is installed, what produce when suppressing to install is crooked extremely important.
When mounted, produce in the semiconductor packages crooked chief reason one of be the coefficient of thermal expansion differences of the silicon chip installed on the surface of employed plywood and this plywood in the semiconductor packages.Therefore, in the semiconductor-sealing-purpose plywood, constantly carrying out making the thermal coefficient of expansion of thermal coefficient of expansion near silicon chip, the i.e. effort of low thermal coefficient of expansionization.In addition, also be crooked because the elastic modelling quantity of plywood hangs down, so making the plywood high resiliencyization in order to reduce bending also is effective.So, in order to reduce the bending of plywood, plywood is carried out low thermal expansionization and high resiliencyization is effective.
Though can expect the multiple method that makes plywood low thermal coefficient of expansionization, high resiliencyization, especially known have the low thermal coefficient of expansionization of the resin that plywood uses and a height fillingization of the inorganic filling material in the resin.Particularly the height fillingization of inorganic filling material is the method (patent documentation 1) that has low thermal coefficient of expansionization and can expect the raising of hear resistance and anti-flammability simultaneously.Yet, for the method for the loading of increase inorganic filling material like this, known its has following situation, promptly, insulating reliability reduces, resin, is being restricted aspect the height fillingization carrying out producing the pressure forming condition of poor when plywood is made with to be formed at connecting airtight of its surperficial wiring layer insufficient.
In addition, the means of reaching low thermal coefficient of expansion by resin choice or improvement have also obtained trial.For example, generally have the crosslink density that improves the resin that distributing board uses, improve Tg and reduce the method (patent documentation 2 and 3) of thermal coefficient of expansion.Yet, though the raising crosslink density can shorten the strand between the functional group, more than strand shortening to a certain degree, aspect reaction, be restricted, also there is the problem that causes that mechanical strength of resin reduces.Therefore, utilizing the method that improves crosslink density to realize also being restricted aspect the low thermal coefficient of expansionization.
So, for plywood in the past,, just progressively reach capacity though realized the low thermal coefficient of expansion high resiliencyization by the height filling and the employing low thermal coefficient of expansion resin of inorganic filling material.
In addition, as being different from above-mentioned method, attempted following method, promptly, use glass-film with the layer of the roughly consistent thermal coefficient of expansion of the thermal coefficient of expansion of electronic unit (silicon chip) as having, thereby by to resin and glass-film pressurization and with its stacked reduction thermal shock stress (patent documentation 4), yet, the thermal coefficient of expansion height because the elastic modelling quantity of resin bed is low is so exist not enough aspect the low bending that realizes substrate.
[technical literature formerly]
[patent documentation]
[patent documentation 1] TOHKEMY 2004-182851 communique
[patent documentation 2] TOHKEMY 2000-243864 communique
[patent documentation 3] TOHKEMY 2000-114727 communique
No. the 4657554th, [patent documentation 4] Japan Patent
The utility model content
[problem that utility model will solve]
As mentioned above, the substrate that the manufacture method by patent documentation 4 obtains remains the low and thermal coefficient of expansion height of elastic modelling quantity, thus realize existing aspect substrate low crooked not enough.
The utility model is In view of the foregoing finished, its purpose is to provide to be had low thermal coefficient of expansion and high elastic modulus and can suppress duplexer crooked, that be suitable for the manufacturing of plywood and multilayer laminate, is difficult for producing plywood and multilayer laminate, the printing distributing board that has used these plywoods and multilayer laminate and the manufacture method of this plywood in crack.
[means that are used to deal with problems]
In patent documentation 4, in the substrate that laminated glass film and resin form, the situation that contains fiber base material in resin is without any record.According to the record of patent documentation 4, what can expect is the situation that should avoid containing fiber base material in resin.
That is, in patent documentation 4, constitute necessary formation (claim 1 of patent documentation 4) by what glass-film came the substantive thermal expansion of determining substrate integral body.Given this, need reduce the influence of resin to the thermal expansion of substrate as far as possible, need to suppress lowly the elastic modelling quantity of resin (if resin has high elastic modulus, then the resin because of this high elastic modulus is a greater impact the thermal expansion of substrate integral body) for this reason.On the other hand, if in resin, contain fiber base material, then can cause the resin high elastic modulusization.Therefore, should avoid containing in the resin fiber base material as can be known according to the record of patent documentation 4.
In addition, if contain fiber base material in the resin of patent documentation 4, what can expect is, fiber base material becomes starting point and glass substrate is easy to generate the situation in crack.Also can infer according to this point and in patent documentation 4, will avoid in resin, containing fiber base material.
Now, for the plywood of such glass-based flaggy of patent documentation 4 and resin bed, there is not the example of the plywood that contains fiber base material in the resin bed.
But, surprisingly, inventors of the present utility model etc. are in order to solve above-mentioned problem and to have carried out lucubrate and found that, in the plywood that comprises resin cured matter layer and glass-based flaggy, contain fiber base material by making in the resin cured matter layer, can obtain to have low thermal coefficient of expansion and high elastic modulus and can suppress crooked and the difficult plywood that produces the crack.
The utility model is finished according to this discovery, with following [1]～[14] as its purport.
[1] a kind of duplexer, it comprises fibrous resin combination layer more than 1 layer and the glass-based flaggy more than 1 layer, described fibrous resin combination layer is made of the heat-curing resin that is dispersed with fiber base material, and described glass-based flaggy is 10～70 volume % with respect to described duplexer integral body.
[2] according to [1] described duplexer, it is characterized in that,
The thickness of described glass-based flaggy is 30～200 μ m.
[3] according to [1] or [2] described duplexer, it is characterized in that,
Described fibrous resin combination layer also is dispersed with inorganic filling material, and with respect to the non-fiber base material composition of removing from fibrous resin combination behind the fiber base material, the content of inorganic filling material is the scope of 5～75 volume %.
[4] according to [1] described duplexer, it is characterized in that,
The width of described duplexer is 10mm～1000mm, and length is 10mm～3000mm, and thickness is 35 μ m～20mm.
[5] according to [1] described duplexer, it is characterized in that,
With respect to the total amount of fibrous resin combination layer, the total content of fiber base material is the scope of 10～80 volume %.
[6] according to [1] described duplexer, it is characterized in that,
Per 1 layer thickness of fibrous resin combination layer is 3 μ m～200 μ m,
Fibrous resin combination layer totally is 4～90 volume % with respect to duplexer.
[7] according to [1] described duplexer, it is characterized in that,
Per 1 layer thickness of glass-based flaggy is 30～200 μ m.
[8] a kind of plywood, it comprises fibrous resin cured matter layer more than 1 layer and the glass-based flaggy more than 1 layer, the serve as reasons solidfied material of the heat-curing resin that is dispersed with fiber base material of described fibrous resin cured matter layer constitutes, and described glass-based flaggy is 10～70 volume % with respect to described plywood integral body.
[9] according to [8] described plywood, it is characterized in that,
The width of described plywood is 10mm～1000mm, and length is 10mm～3000mm, and thickness is 35 μ m～20mm.
[10] according to [8] described plywood, it is characterized in that,
The thickness of described fibrous resin cured matter layer is 3～200 μ m.
[11] according to [8] described plywood, it is characterized in that,
The thickness of described glass-based flaggy is 30～200 μ m.
[12] a kind of multilayer laminate, it comprises a plurality of plywoods, wherein, at least one plywood is any described plywood in [8]～[11].
[13] a kind of printing distributing board, it has any described plywood and the lip-deep distribution that is arranged on described plywood in [8]～[11].
[14] a kind of printing distributing board, the lip-deep distribution that it has [12] described multilayer laminate and is arranged on described multilayer laminate.
[utility model effect]
According to the utility model, can provide to have low thermal coefficient of expansion and high elastic modulus and can suppress crooked and be difficult for producing the plywood and the multilayer laminate in crack, the duplexer that is suitable for making these plywoods and multilayer laminate, the printing distributing board that has used these plywoods and multilayer laminate, and the manufacture method of this plywood.
Description of drawings
Fig. 1 is the schematic cross sectional views that relates to the duplexer of the 1st embodiment.
Fig. 2 is the schematic cross sectional views that relates to the duplexer of the 2nd embodiment.
Fig. 3 is the schematic cross sectional views that relates to the duplexer of the 3rd embodiment.
Fig. 4 is the schematic cross sectional views that relates to the plywood of the 1st embodiment.
Fig. 5 is the schematic cross sectional views that relates to the plywood of the 2nd embodiment.
Fig. 6 is the schematic cross sectional views that relates to the plywood of the 3rd embodiment.
Symbol description
10 duplexers
11a, 11b, 11c, 11d resin combination layer
12 glass-based flaggies
20 duplexers
21a, 21b resin combination layer
22 glass-based flaggies
30 duplexers
31a, 31b, 31c resin combination layer
32a, 32b glass-based flaggy
110 plywoods
111a, 111b, 111c, 111d resin cured matter layer
112 glass-based flaggies
120 plywoods
121a, 121b resin cured matter layer
122 glass-based flaggies
130 plywoods
131a, 131b, 131c resin cured matter layer
132a, 132b glass-based flaggy
The specific embodiment
Below, be elaborated for the manufacture method of duplexer of the present utility model, plywood, multilayer laminate, printing distributing board and plywood.
Need to prove that in the utility model, duplexer is meant, is the duplexer of uncured or semi-solid preparation as the heat-curing resin of its constituent, and plywood is meant, the plywood that solidifies takes place as the heat-curing resin of its constituent.
[duplexer]
Duplexer of the present utility model is to comprise the resin combination layer more than 1 layer and the duplexer of the glass-based flaggy more than 1 layer, described fibrous resin combination layer is made of the heat-curing resin that is dispersed with fiber base material, and described glass-based flaggy is 10～70 volume % with respect to described duplexer integral body.
For the size of duplexer of the present utility model, from the viewpoint of operability, preferably at width 10mm～1000mm, the scope of length 10mm～3000mm (under situation about using with web-like, length can suitably be suitable for) is selected.Be preferably width 25mm～550mm, the scope of length 25mm～550mm especially.
The thickness of duplexer of the present utility model according to its purposes, is preferably selected in the scope of 35 μ m～20mm.The thickness of duplexer is 50～1000 μ m more preferably, and more preferably 80～600 μ m especially are preferably 100～500 μ m, are preferably 110～450 μ m especially.
Duplexer of the present invention is to comprise the resin combination layer more than 1 layer and the duplexer of the glass-based flaggy more than 1 layer, described resin combination layer is served as reasons and is comprised the fibrous resin combination formation of heat-curing resin and fiber base material, and described glass-based flaggy totally is 10～70 volume % with respect to described duplexer.
Be used as for the plywood that fibrous resin cured matter layer obtains for solidifying by the fibrous resin combination layer that makes duplexer of the present utility model, owing to have and the low thermal coefficient of expansion of silicon chip same degree and the glass-based flaggy of high elastic modulus, so become the works of low thermal coefficient of expansion and high elastic modulus, thereby can suppress crooked and the difficult crack that produces.Especially, because this plywood has the high glass-based flaggy of hear resistance, so, in temperature province, have significant low heat expansion from 100 ℃ less than the Tg of fibrous resin cured matter.In addition, owing in fibrous resin cured matter layer, contain fiber base material, so fibrous resin cured matter layer becomes the layer structure of low thermal coefficient of expansion and high elastic modulus, thereby make the plywood that comprises this fibrous resin cured matter layer become the material of further low thermal expansion and high elastic modulus.
In addition, as long as have said structure, duplexer of the present utility model also can have not fibrous resin combination layer except the resin combination layer of the fiber containing base material more than 1 layer and the glass-based flaggy more than 1 layer.But from making the viewpoint of less thick, duplexer preferably is made of fibrous resin combination layer more than 1 layer and the glass-based flaggy more than 1 layer.Similarly, from making the viewpoint of less thick, plywood described later preferably is made of fibrous resin cured matter layer more than 1 layer and the glass-based flaggy more than 1 layer.
＜fibrous resin combination 〉
Fibrous resin combination of the present utility model comprises heat-curing resin and fiber base material.
" heat-curing resin "
There is no particular restriction as heat-curing resin, for example can enumerate epoxy resin, phenolic resins, unsaturated acyl imide resin, cyanate ester resin, isocyanate resin, benzoxazine colophony, oxetane resin, amino resins, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, silicone resin, cyanate resin, melamine resin.From formability, the good point of electrical insulating property, wherein preferred epoxy and cyanate ester resin.
As epoxy resin, for example, can list bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol novolak type epoxy resin, the cresols phenolic resin varnish type epoxy resin, bisphenol-A phenolic varnish type epoxy resin, bisphenol F phenolic varnish type epoxy resin, talan type epoxy resin, the epoxy resin that contains the triazine skeleton, the epoxy resin that contains fluorene skeleton, triphenol methane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, alicyclic epoxy resin, the diglycidyl ether compound of the Ppolynuclear aromatic class of multifunctional phenol and anthracene etc.In addition, can also list the phosphorous epoxy resin that has imported phosphorus compound to these epoxy resin.Wherein, consider preferred biphenyl aralkyl type epoxy resin and naphthalene type epoxy resin from hear resistance, anti-flammability aspect.Mixing more than a kind or 2 kinds in them can be used.
As cyanate ester resin, for example, can list the bisphenol type cyanate ester resin of phenolic varnish type cyanate ester resin, bisphenol A cyanate ester resin, bisphenol E-type cyanate resin, tetramethyl Bisphenol F type cyanate ester resin etc., their a part of triazine changes prepolymer.Wherein, consider preferred phenolic varnish type cyanate ester resin from hear resistance, anti-flammability aspect.Mixing more than a kind or 2 kinds in them can be used.
With respect to the quality of from the total amount of fibrous resin combination, removing the non-fiber base material composition behind the fiber base material, the content of contained heat-curing resin is preferably the scope of 20～80 quality % in the fibrous resin combination, 25～60 quality % more preferably, more preferably 25～50 quality % especially are preferably 25～40 quality %.
" fiber base material "
Be not particularly limited as fiber base material, can enumerate inorganic matter fibers such as E glass, D glass, S glass and Q glass, the organic fiber of polyimides, polyester and polytetrafluoroethylene (PTFE) etc., and their mixture etc.These fiber base materials for example have weave cotton cloth, the shape of adhesive-bonded fabric, rove, chopped strand mat and face felt etc., but can select material and shape according to the purposes and the performance of the shaping thing of purpose, as required, above material and the shape of 2 kinds alone or in combination.
The thickness of base material is not particularly limited, and for example, can use about 0.03～0.5mm, and from hear resistance, moisture-proof, the aspect of processability considers, is suitably with silane coupler etc. to have carried out the surface-treated material or mechanically implemented to open the fine material of handling.
Total amount with respect to fibrous resin combination, the total content of fiber base material is preferably the scope of 10～80 volume %, more preferably 15～75 quality %, more preferably 20～70 quality %, more preferably 30～60 quality %, more preferably 30～55 quality %.
" inorganic filling material "
Fibrous resin combination can further contain inorganic filling material.
Contain in fibrous resin combination under the situation of inorganic filling material, with respect to the non-fiber base material composition of removing from fibrous resin combination behind the fiber base material, the content of inorganic filling material is preferably the scope of 5～75 volume %.In addition, with respect to the non-fiber base material composition of removing from fibrous resin combination behind the fiber base material, the content of inorganic filling material is 15～70 quality % more preferably, more preferably 30～70 quality %.As inorganic filling material, for example, can list silica, aluminium oxide, talcum, mica, aluminium hydroxide, magnesium hydroxide, calcium carbonate, aluminium borate, borosilicate glass etc.
Wherein, consider preferred silica from the low heat expansion aspect, further preferred thermal coefficient of expansion is that this very little and flowability when resin carried out high filling the in the 0.6ppm/K left and right sides reduces little spherical amorphous silica.
As spherical amorphous silica, accumulating 50% particle diameter is 0.01～10 μ m, is preferably 0.03～5 μ m.
At this, accumulating 50% particle diameter is meant, when the whole volumes with powder be 100% obtain based on particle diameter the accumulation number of degrees distribution curve time, just in time be equivalent to the situation of the particle diameter of volume 50% this point, can wait by the particle size distribution device that has utilized laser diffraction method at random and measure.
In addition, be silica (nano silicon) below the 1 μ m by in inorganic filling material, using average primary particle diameter, can on the fibrous resin cured matter layer of plywood, form trickle distribution.As nano silicon, specific area is preferably 20m 2More than/the g.In addition, the viewpoint that the surface configuration after the roughening treatment from plating technic diminishes, average primary particle diameter is preferably below the 100nm.This specific area can be measured by the BET method.
In addition, " average primary particle diameter " described herein is not the average diameter of the particle after the aggegation, i.e. aggregate particle size, but the average grain diameter of UA free state.This average primary particle diameter for example, can be measured by laser diffraction formula size distribution meter and obtain.Inorganic filling material as such is preferably pyrogenic silica.
In addition, for inorganic filling material,, preferably handle,, preferably carry out hydrophobization and handle in order to improve dispersiveness with the surface conditioning agent of silane coupler etc. in order to improve moisture-proof.
Under the situation that forms trickle distribution on the fibrous resin cured matter layer of plywood, the content of inorganic filling material is preferably below the 20 quality % in the non-fibre composition of removing from fibrous resin combination behind the fiber base material.If use level is below the 20 quality %, then can keep the surface of good shape after the roughening treatment, can prevent the reduction of the insulating reliability of plating characteristic and interlayer.On the other hand, owing to can expect low-thermal-expansionization, the high resiliencyization of fibrous resin combination by containing inorganic filling material, therefore pay attention to when forming trickle distribution under the situation of low-thermal-expansionization, high resiliencyization, the content of inorganic filling material is preferably 3～20 quality %.
" other compositions "
In this fibrous resin combination, except mentioned component, can also add curing agent, curing accelerator, thermoplastic resin, elastomer, fire retardant, ultra-violet absorber, antioxidant, Photoepolymerizationinitiater initiater, fluorescent whitening agent, connecting airtight property improving agent etc.
As the example of curing agent, for example, under the situation that adopts epoxy resin, can use multifunctional phenolic compounds such as phenol novolaks, cresols novolaks; Amines such as cdicynanmide, MDA, diamino diphenyl sulfone; The acid anhydrides of phthalic anhydride, PMDA, maleic anhydride, maleic anhydride copolymers etc.; Polyimides.Can and several with in these curing agent.
As the example of curing accelerator, for example can list imidazoles and derivative thereof as the curing accelerator of epoxy resin; The organophosphor based compound; Secondary amine class, tertiary amines and quaternary ammonium salt.
As the example of ultra-violet absorber, can list the ultra-violet absorber of BTA system.
As antioxidant, can list the antioxidant of hindered phenol system or SP styrenated phenol.
As the example of Photoepolymerizationinitiater initiater, can list the Photoepolymerizationinitiater initiater of Benzophenone class, benzyl ketals class, thioxanthones system.
As the example of fluorescent whitening agent, can list the fluorescent whitening agent of diphenyl ethylene derivatives.
As the example of connecting airtight property improving agent, can list the connecting airtight property improving agent of urea compounds, silane couplers etc. such as urea silane.
＜fibrous resin combination layer 〉
Fibrous resin combination layer is made of above-mentioned fibrous resin combination.Need to prove, in fibrous resin combination layer, except the uncured thing of fibrous resin combination, also comprise the semi-solid preparation thing.
For the size of fibrous resin combination layer of the present utility model, preferably at width 10mm～1000mm, the scope of length 10mm～3000mm (under situation about using with web-like, length can suitably be suitable for) is selected.Viewpoint from operability is preferably especially, width 25mm～550mm, the scope of length 25mm～550mm.
Per 1 layer thickness of fibrous resin combination layer of the present utility model is preferably selected in the scope of 3 μ m～200 μ m.From the low-thermal-expansionization of duplexer and plywood, the viewpoint of high elastic modulusization, per 1 layer thickness of resin combination is preferably 3～150 μ m, 10～120 μ m more preferably, and more preferably 20～120 μ m are preferably 25～110 μ m especially.
Fibrous resin combination layer of the present utility model is contained with respect to the overall preferred ratio with 4～90 volume % of duplexer, more preferably with 30～90 volume %, further preferably with 30～85 volume %, especially preferably the ratio with 30～80 volume % is contained.
In addition, duplexer of the present invention and plywood have the resin combination layer of 1 layer fiber containing base material at least, also can have the not resin combination layer of fiber containing base material in addition.The resin combination layer of fiber containing base material for example can not dispose between the resin combination layer of glassy layer and fiber containing base material, to improve purposes such as two-layer cementability and use.
The dried resin containing ratio of this fibrous resin combination layer is preferably 20～90 quality %, more preferably more than 25～85 quality %, more preferably 30～80 quality %, more preferably 40～70 quality %, more preferably 45～70 quality %.If more than the 20 quality %, then improve processability and operability (processing easiness).If below the 90 quality %, then the content of fiber base material is more, the fibrous resin combination layer of this duplexer is solidified the plywood that forms become low thermal coefficient of expansion and elastomeric material.Need to prove that the resin containing ratio is meant the one-tenth component except that fiber base material in the total amount of fibrous resin combination.
In addition, when containing inorganic filling material in the fibrous resin combination, be preferably 5～75 volume % of total metering of heat-curing resin and inorganic filling material, more preferably 15～70 volume %, more preferably 30～70 volume %.If the content of inorganic filling material is 5～75 volume % of total metering of heat-curing resin and inorganic filling material, then thermal coefficient of expansion low to subtract effect abundant, and have the flowability of appropriateness, thereby have excellent moldability.That is, if the content of inorganic filling material is more than the 5 volume %, then thermal coefficient of expansion low to subtract effect abundant, if below the 75 volume %, thereby then mobile to increase formability good.
＜glass-based flaggy 〉
As the glass substrate that constitutes the glass-based flaggy, consider from the viewpoint of the slimming of reaching duplexer and processability, the slimming glass-film of preferred 30～200 μ m of per 1 layer thickness of glass-based flaggy, consider the practicality such as easiness of processing, thickness is more preferably 30～150 μ m, more preferably 80～120 μ m.The thickness of glass-based flaggy described herein is meant the average thickness of glass-based flaggy.The average thickness of glass-based flaggy can use the known thickness measurement machine of micrometer, determining film thickness device etc. to measure.For example, under the situation that is rectangle or foursquare glass-based flaggy, use micrometer to measure 4 jiaos and central thickness, its mean value is obtained as the average thickness of glass-based flaggy.
In addition, as the raw material of glass baseplate, can use silicate base is the glass of glass, alkali-free glass, quartz glass etc., considers preferred borosilicate glass from the viewpoint of low heat expansion.
For the size of glass-based flaggy of the present utility model, preferably at width 10mm～1000mm, the scope of length 10mm～3000mm (under situation about using with web-like, length can suitably be suitable for) is selected.Viewpoint from operability is preferably especially, width 25mm～550mm, the scope of length 25mm～550mm.
For the thermal coefficient of expansion of this glass-based flaggy, the bending of the plywood that then can suppress duplexer more near the thermal coefficient of expansion (about 3ppm/ ℃) of silicon chip more or obtain by this duplexer, but it is preferably below 8ppm/ ℃, more preferably below 6ppm/ ℃, further more preferably below 4ppm/ ℃.
For the storage elastic modelling quantity under 40 ℃ of this glass-based flaggy, it is the bigger the better, but is preferably more than the 20GPa, more preferably more than the 25GPa, further more preferably more than the 30GPa.
This glass-based flaggy is preferably 10～70 volume % with respect to duplexer integral body, more preferably 15～70 volume %, more preferably 20～70 volume %.If the content of glass-based flaggy is more than the 10 volume %, then obtain aspect low heat expansion, the elastomeric duplexer favourable, opposite if the content of glass-based flaggy is below the 70 volume %, then favourable on the point of processability, operability (easiness of processing).
＜supporting mass film 〉
Above-mentioned duplexer can have the supporting mass film on its surface.For this supporting mass film, in the explanation that the following manufacture method to duplexer is carried out, will be described in detail.
[manufacture method of duplexer]
Manufacture method for above-mentioned duplexer does not have particular restriction, can make aptly by stacked prepreg and the glass substrate that is made of fibrous resin combination.
As this laminating method, for example suitable such pressurization lamination of vacuum lamination described later, roll-in lamination etc. of using.
＜prepreg 〉
Prepreg can obtain by the following method aptly, after being about to contain the resin combination impregnation of described heat-curing resin and described inorganic filling material as required or being coated on the fiber base material, makes it B stageization (semi-solid preparation) by heat drying.This B stageization, usually can by under 100～200 ℃ the temperature, heat drying carries out about 1～30 minute.
＜pressurization lamination 〉
The pressurization lamination can be by using vacuum laminator, the such pressurization laminator of roll-in laminator, will carry out lamination by the overlapping prepreg polymer that forms of prepreg of 1 prepreg or multi-disc (for example 2～20) and glass substrate and carry out.Vacuum lamination, roll-in lamination can use vacuum laminator, the roll-in laminator peddled on the market to carry out.
Need to prove, as the heat-curing resin in the above-mentioned fibrous resin combination, the suitable material that uses the following fusion of temperature when lamination.For example, using vacuum laminator or roll-in laminator to carry out under the situation of lamination, generally carrying out below 140 ℃, so the heat-curing resin in the above-mentioned fibrous resin combination is preferably in fusion below 140 ℃.
" supporting mass film "
The prepreg that uses in the lamination preferably disposes the supporting mass film at single face.
As the supporting mass film, can list for example polyethylene, polyvinyl chloride etc. polyolefin, PETG (below, omission is called " PET "), polyester, Merlon, the polyimides of PEN etc., further can list processing release paper or metal formings such as Copper Foil, aluminium foil.Under the situation of using Copper Foil to use, Copper Foil directly can be formed the loop as conductor layer as the supporting mass film.In this case, as Copper Foil, can list calendering copper, electrolytic copper foil etc., general used thickness is the Copper Foil of 2 μ m～36 μ m.Under the situation of the thin Copper Foil of used thickness,, can use the band carrier copper foil in order to improve operation.
For the supporting mass film, except hair side processing, sided corona treatment, also can implement the demoulding and handle.
The thickness of supporting mass film is generally 10 μ m～150 μ m, is preferably 25～50 μ m.Under than the thin situation of 10 μ m, having difficulties aspect the property handled.On the other hand, the such as described common quilt of supporting mass film is finally peeled off or is removed, if thickness surpasses 150 μ m, considers not preferred from saving viewpoint of energy.
" concrete example of pressurization lamination "
Below, the concrete example of pressurization lamination method is described.
Will be with the prepreg of supporting mass film while pressurizeing and heating, carry out crimping to glass substrate.About the condition of lamination, as required with prepreg and glass substrate preheating, crimping temperature (lamination temperature) is preferably 60 ℃～140 ℃, and crimping pressure is preferably 1～11kgf/cm 2, preferably under such condition, carry out lamination.In addition, under the situation of using the vacuum laminator, preferably under the decompression below the air pressure 20mmHg (26.7hPa), carry out lamination.In addition, the method for lamination can be batch (-type), also can be the continous way of utilizing roller to carry out.
As described above, with prepreg after the glass substrate lamination, be cooled near room temperature.Can make duplexer like this.
[plywood]
Plywood of the present utility model is to comprise the resin cured matter layer more than 1 layer and the plywood of the glass-based flaggy more than 1 layer, the serve as reasons solidfied material of the heat-curing resin that is dispersed with fiber base material of described fibrous resin cured matter layer constitutes, and described glass-based flaggy is 10～70 volume % with respect to described plywood integral body.
For the size of plywood of the present utility model, preferably at width 10mm～1000mm, the scope of length 10mm～3000mm (under situation about using with web-like, length can suitably be suitable for) is selected.Viewpoint from operability is preferably especially, width 25mm～550mm, the scope of length 25mm～550mm.
The thickness of plywood of the present utility model according to its purposes, is preferably selected in the scope of 35 μ m～20mm.The thickness of plywood is 50～1000 μ m more preferably, and more preferably 80～600 μ m especially are preferably 100～500 μ m, are preferably 110～450 μ m especially.
This plywood is preferably makes structure behind the fibrous resin cured matter layer with the fibrous resin combination layer of above-mentioned duplexer.At this moment, the details of this glass-based flaggy and fibrous resin combination is identical with situation about illustrating in aforesaid record about duplexer.In addition, the thickness of fibrous solidfied material layer preferably is equal to the thickness of aforesaid fibrous composition layer, the fibrous resin cured matter in the plywood and the ratio of glass-based flaggy preferably with aforesaid duplexer in the fibrous resin solidfied material and the ratio of glass-based flaggy be equal to.
＜fibrous resin cured matter layer 〉
The thickness of this fibrous resin cured matter layer is preferably 3～200 μ m.If more than the 3 μ m, then the crack of plywood can be inhibited.If below the 200 μ m, then relatively the thickness of glass substrate becomes big, thereby can realize the low thermal coefficient of expansionization and the high elastic modulusization of plywood.According to this viewpoint as can be known, the thickness of fibrous resin cured matter layer is 3～150 μ m more preferably, further more preferably 10～120 μ m, more preferably 20～120 μ m, more preferably 25～110 μ m.But, different according to the kind of the thickness of glass-based flaggy and the number of plies and fibrous resin cured matter layer and the number of plies, the proper range of the thickness of fibrous resin cured matter layer is different, therefore also can adjust aptly.。
Storage elastic modelling quantity under 40 ℃ of this fibrous resin cured matter layer is preferably 10～80GPa.If more than the 10GPa, then the glass-based flaggy is protected, and the crack of plywood is inhibited.If below the 80GPa, then the stress that produces because of the coefficient of thermal expansion differences of glass-based flaggy and fibrous resin cured matter layer is inhibited, thereby the bending of plywood and crack are inhibited.According to this viewpoint as can be known, the storage elastic modelling quantity of fibrous resin cured matter layer is preferably 12～75GPa, is more preferably 15～70GPa.
Single face or two sides at plywood can have metal formings such as copper, aluminium or nickel.Metal forming can be used for the electrically insulating material purposes and get final product, and it is not had particular restriction.
The characteristic of＜plywood 〉
From the bending that suppresses plywood and the viewpoint in crack, the storage elastic modelling quantity under 40 ℃ of plywood is preferably 10～70GPa, 20～60GPa more preferably, and more preferably 25～50GPa especially is preferably 25～45GPa.
From the bending of inhibition plywood and the viewpoint in crack, average thermal coefficient of expansion in 50～120 ℃ the scope of plywood is preferably 1～10ppm/ ℃, more preferably 2～8ppm/ ℃, more preferably 2～6ppm/ ℃, especially be preferably 2～5ppm/ ℃.
From the bending of inhibition plywood and the viewpoint in crack, average thermal coefficient of expansion in 120～190 ℃ the scope of plywood is preferably 1～15ppm/ ℃, more preferably 2～10ppm/ ℃, more preferably 2～8ppm/ ℃, especially be preferably 2～6ppm/ ℃.
[manufacture method of plywood]
Manufacture method to above-mentioned plywood is not particularly limited.Below, the concrete example of the manufacture method of plywood is described.
＜utilize the Production Example that is heating and curing of the duplexer that obtains by lamination 〉
In the duplexer that utilizes described lamination to obtain, after peeling off the supporting mass film as required, be heating and curing by making fibrous resin combination layer, can make plywood.
The condition that is heating and curing can be selected in 150 ℃～220 ℃ following 20 minutes～80 minutes scopes, and more preferably 160 ℃～200 ℃ following 30 minutes～120 minutes.Implemented in use after also can making it to be heating and curing, to peel off the supporting mass film again under the situation of the supporting mass film that the demoulding handles.
By this method,, can suppress to produce during fabrication the crack owing to when the manufacturing of plywood, need not pressurization.
＜based on the Production Example of pressing method 〉
In addition, plywood of the present utility model can be made by the pressing method.
For example, by the pressing method duplexer that utilizes described lamination to obtain is heated, pressurizes, makes its curing, thereby can make plywood.
In addition, also can heat, pressurize by the pressing method, make it to solidify, make plywood by 1 the prepreg or the overlapping prepreg polymer and the glass substrate that forms of prepreg of multi-disc (for example 2～20) are overlapped.At this moment, can further behind the surperficial apposition supporting mass film of outermost prepreg, heat, pressurize, make it to solidify, make plywood by the pressing method.
This pressing method from the aspect that is shaped equably for preferably, but since when stacked glass substrate break easily, stacked condition is restricted.On the other hand, as described above, the autofrettage of be heating and curing (the lamination method) of the duplexer that utilization is obtained by lamination is set out aspect being not easy in crack, the production to be easy to preferably at glass substrate, but, there is the shaping situation of difficult sometimes along with the proterties or the content of fibrous resin combination and fiber base material are different.Therefore, preferably as required pressing method and lamination method are used flexibly.
[multilayer laminate and manufacture method thereof]
Multilayer laminate of the present utility model is the multilayer laminate that comprises a plurality of plywoods, and at least one plywood is aforesaid plywood of the present utility model.
Manufacture method for this multilayer laminate does not have particular restriction.
For example, by the described duplexer of overlapping, stacked shaping multi-disc (for example, 2～20), can make multilayer laminate.Particularly, can use multistage pressing, multi-stage vacuum pressing, progressive forming machine, autoclave forming machine etc., about about 100～250 ℃ of temperature, pressure 2～100MPa, and 0.1～5 hour heat time heating time about scope in form.
[printing distributing board and manufacture method thereof]
Printing distributing board of the present utility model has above-mentioned plywood or multilayer laminate and is arranged on plywood or the distribution on the surface of multilayer laminate.
Next, the manufacture method to this printing distributing board describes.
The formation of＜through hole etc. 〉
Can carry out perforate to above-mentioned plywood by drilling machine, laser, plasma or their methods such as combination as required, thereby form through hole or open-work.As laser, generally use carbonic acid gas laser, YAG laser, UV laser, PRK etc.
The formation of＜conductor layer 〉
Next, on the fibrous resin cured matter layer of plywood, form conductor layer by dry type plating or wet type plating.
As the dry type plating, can use known method such as evaporation, sputter, ion plating.
For the situation of wet type plating, at first, utilize permanganate (potassinm permanganate, sodium permanganate etc.), bichromate, ozone, hydrogen peroxide/sulfuric acid (promptly, the mixture of hydrogen peroxide and sulfuric acid), the oxidant of nitric acid etc. carries out roughening treatment to the surface of the fibrous resin cured matter layer that solidified, thereby forms the asperities (anchor) of convex-concave.As oxidant, especially preferably use the sodium hydrate aqueous solution (alkalescence is crossed the mangaic acid aqueous solution) of potassinm permanganate, sodium permanganate etc.Next, utilize method to form conductor layer with electroless plating applies and the electrolysis plating makes up.In addition, form the plating layer that prevents with the conductor layer opposite pattern, form conductor layer thereby can only apply with electroless plating.
Need to prove,, use to have under the situation of the supporting mass film that constitutes by metal forming, can omit the formation operation of this conductor layer on the surface as duplexer.
The formation of＜Wiring pattern 〉
As the method that thereafter pattern forms, for example can use known removal method (subtractive process), semi-additive process etc.
[multi-layer printed circuit board and manufacture method thereof]
As a form of above-mentioned printing distributing board, can multilayer laminatedly as described above form Wiring pattern plywood and as multi-layer printed circuit board.
When making this multi-layer printed circuit board, carry out the multilayer laminated multiple stratification that realizes across aforesaid bonding film by the plywood that will be formed with above-mentioned Wiring pattern.Then, form open-work or blind via hole, form the interlayer distribution by plating or conductive paste by drilling machine processing or Laser Processing.So, can make multi-layer printed circuit board.
[band plywood of metal forming and multilayer laminate, and their manufacture method]
Need to prove that described plywood and multilayer laminate can be plywood and the multilayer laminate that has the band metal forming of metal formings such as copper, aluminium or nickel on single face or two sides.
Manufacture method for the plywood of this band metal forming does not have particular restriction.For example, use metal forming as the supporting mass film like that as described above, can make the plywood of band metal forming thus.In addition, the duplexer overlapping one or more pieces (for example 2～20) that will obtain by described lamination utilizes the structure that disposes metal forming on its single face or two sides to carry out stacked shaping, can make the plywood that has metal forming thus.
About molding condition, can be suitable for electrically insulating material plywood, multiple-plate method, for example, use multistage pressing, multi-stage vacuum pressing, progressive forming machine, autoclave forming machine etc. about about 100～250 ℃ of temperature, pressure 2～100MPa, and 0.1～5 hour heat time heating time about scope in form.
The evaluation method of＜thermal coefficient of expansion 〉
The thermal coefficient of expansion of plywood can use the device of three-dimensional displacement determinator (DIC:Degital Image Correlation), laser interferance method of thermo-mechanical analysis device (TMA:Thermal Mecanical Aanlysis), temperature dependent etc. to measure.
The evaluation method of＜elastic modelling quantity 〉
For the elastic modelling quantity of plywood, except the storage Determination of Modulus of utilizing wide area determination of viscoelasticity device, can measure the modulus of elasticity in static bending as static modulus of elasticity.The modulus of elasticity in static bending can be obtained by carrying out 3 bend tests etc.
[stepped construction of duplexer]
As the stepped construction of duplexer, as previously mentioned, as long as, just be not particularly limited for comprising the resin combination layer more than 1 layer and the stepped construction of the glass-based flaggy more than 1 layer.
For example, as shown in Figure 1, can be the duplexer 10 of 5 layers of structure that resin combination layer 11a, resin combination layer 11b, glass-based flaggy 12, resin combination layer 11c, resin combination layer 11 form with this sequential cascade.
In addition, as shown in Figure 2, can be the duplexer 20 of the 3-tier architecture that resin combination layer 21a, glass-based flaggy 22, resin combination layer 21b form with this sequential cascade.
In addition, as described in Figure 3, can be the duplexer 30 of 5 layers of structure that resin combination layer 31a, glass-based flaggy 32a, resin combination layer 31b, glass-based flaggy 32b, resin combination layer 31c form with this sequential cascade.
[stepped construction of plywood]
As the stepped construction of plywood, as previously mentioned, as long as, just be not particularly limited for comprising the resin cured matter layer more than 1 layer and the stepped construction of the glass-based flaggy more than 1 layer.
For example, as shown in Figure 4, can be the plywood 110 of 5 layers of structure that resin cured matter layer 111a, resin cured matter layer 111b, glass-based flaggy 112, resin cured matter layer 111c, resin cured matter layer 111 form with this sequential cascade.
In addition, as shown in Figure 5, can be the plywood 120 of the 3-tier architecture that resin cured matter layer 121a, glass-based flaggy 122, resin cured matter layer 121b form with this sequential cascade.
In addition, as described in Figure 6, can be the plywood 130 of 5 layers of structure that resin cured matter layer 131a, glass-based flaggy 132a, resin cured matter layer 131b, glass-based flaggy 132b, resin cured matter layer 131c form with this sequential cascade.
[embodiment]
Below, use embodiment and comparative example that the utility model is illustrated in greater detail, but the utility model is not subjected to the qualification of these records.
Need to prove that in embodiment and comparative example, " part " reaches " % " and means that respectively " mass parts " reaches " quality % ".
＜have a manufacturing of solution of the resin combination of unsaturated maleimide base 〉
In being 2 liters reaction vessel, the volume that can heat and cool off that has thermometer, agitating device, backflow cooling tube and band water and basis weight device puts into 4,4 '-two (4-amino-benzene oxygen) biphenyl: 69.10g, two (4-maleimide phenyl) sulfone: 429.90g, para-aminophenol: 41.00g, and propylene glycol monomethyl ether: 360.00g, reaction is 2 hours under reflux temperature, thereby acquisition has the solution of the resin combination of acid substituting group and unsaturated maleimide base.
＜contain the manufacturing of the varnish of hot curing resin composition 〉
(1) as curing agent (A), use the solution of resin combination with above-mentioned unsaturated maleimide base,
(2) as heat-curing resin (B), use 2 functional group's naphthalene type epoxy resin (big Japanese ink chemical industry (strain) system, trade name, HP-4032D),
(3) as modified imidazole (C), use isocyanates sealing imidazoles (Japanese: イ ソ シ ア ネ one ト マ ス Network イ ミ ダ ゾ one Le) (the first industrial pharmacy (strain) system, trade name: G8009L),
(4) as inorganic filling material (D), and the use fused silica (Admatech (strain) system, trade name: SC2050-KC, concentration 70%, the average grain diameter of primary particle: 500nm is based on the specific area of BET method: 6.8m 2/ g),
(5) as giving the phosphorus-containing compound (E) of anti-flammability, use phosphorus containing phenolic resin (three photochemistry (strain) system, trade name: HCA-HQ, phosphorus content 9.6 quality %),
(6) as the possible compound of chemical roughen (F), use crosslinking acrylonitrile butadiene (NBR) particle [(JSR (strain) system, trade name: XER-91),
(7) as retarder thinner, use methyl ethyl ketone,
Carrying out (mass parts) according to the cooperation ratio shown in the table 1 and mix, is 65 quality % thereby produce resin content (total of resinous principle), and solvent is the uniform varnish (G) of 35 quality %.
[table 1]
Table 1
Mass parts
Curing agent (A) 50
Heat-curing resin (B) 49.5
Modified imidazole (C) 0.5
Inorganic filling material (D) 40
Phosphorus-containing compound (E) 3
Compound (F) 1
The manufacturing of＜prepreg 〉
To the different E glass fabric of thickness respectively impregnation be coated with above-mentioned varnish (G), 160 ℃ of following heat dryings 10 minutes, thereby obtain the prepreg of 250mm * 250mm.Kind about the E glass fabric, use 3 kinds of IPC specification 1027,1078,2116 of the Japanese イ of Asahi Chemical Industry one マ テ リ ア Le ズ company, use that the resin content of the prepreg (being called PP#1027, PP#1078, PP#2116 sometimes) that the glass fabric of these 3 kinds makes is respectively 66,54, and 50 quality %.The E glass fabric content of these prepregs is respectively 34,46 and 50 quality % in addition.
[embodiment 1～6 and comparative example 1]
As glass-film, glass-film " trade name OA-10G " (NEG (strain) system, 250mm * 250mm) and the glass-film " trade name OA-10G " of thickness 100 μ m (NEG (strain) the system 250mm * 250mm) (be called GF50 μ m and GF100 μ m sometimes) of thickness 50 μ m have been prepared.
With above-mentioned glass-film and described prepreg, the as shown in table 2 coincidence at the electrolytic copper foil of upper and lower configuration thickness 12 μ m, carried out pressurization in 120 minutes under 235 ℃ of pressure 3.0MPa, temperature, make the copper-clad lamination.
[mensuration]
For the plywood that in the above embodiments, comparative example, obtains, measure and estimate its performance by following method.
(1) mensuration of thermal coefficient of expansion
Cut out the test film of 4mm * 30mm from plywood.Under the situation of using the copper-clad lamination,, cut out test film then by being immersed in the copper etchant solution and eliminating Copper Foil.
(the DuPont corporate system TMA2940), is estimated less than the thermal expansion character of the Tg of test film by observation to use the TMA experimental rig.Particularly, 5 ℃/min of programming rate, the first round, 20～200 ℃ of measurement ranges, second takes turns, measurement range-10～280 ℃, increase the weight of 5g, 10mm between anchor clamps measures by pulling method with this, thereby obtains the average thermal coefficient of expansion of the scope of 50～120 ℃ scope and 120～190 ℃ respectively.Its result is shown in the table 2.
(2) storage Determination of Modulus
Cut out the test film of 5mm * 30mm from plywood.Under the situation of using the copper-clad lamination, by be immersed in remove Copper Foil in the copper etchant solution after, cut out test film again.
Use wide area determination of viscoelasticity device (Japanese レ オ ロ ジ society system, DVE-V4 type), under the condition with spacing 20mm, frequency 10Hz, vibration displacement 1～3 μ m (failure of oscillations), elastic modelling quantity is stored in stretching down to have measured 40 ℃.Its result is table 2 illustrate.
[table 2]
Figure BDA00002174309200221
According to table 2 can be clear and definite be that the embodiment of the present utility model 1～6 that contains glass-film compares with the comparative example 1 that does not contain glass-film, and is superior aspect the high resiliency under the low heat expansion under 50～120 ℃, 40 ℃.In addition we know, at 120～190 ℃ high-temperature area,, in embodiment 1～6, has low heat expansion with the roughly the same degree of low-temperature region with respect to comparing the situation that thermal coefficient of expansion rises to some extent with low-temperature region (50～120 ℃) in the comparative example 1.Therefore, embodiment 1～6 of the present utility model not only also keeps low heat expansion at low-temperature region but also at high-temperature area.

Claims (14)

1. duplexer, it comprises fibrous resin combination layer more than 1 layer and the glass-based flaggy more than 1 layer, described fibrous resin combination layer is for to contain the prepreg that is soaked with heat-curing resin on fiber base material, described glass-based flaggy is 10～70 volume % with respect to described duplexer integral body.
2. duplexer according to claim 1 is characterized in that,
The thickness of described glass-based flaggy is 30～200 μ m.
3. duplexer according to claim 1 and 2 is characterized in that,
The width of described duplexer is 10mm～1000mm, and length is 10mm～3000mm, and thickness is 35 μ m～20mm.
4. duplexer according to claim 1 and 2 is characterized in that,
Per 1 layer thickness of fibrous resin combination layer is 3 μ m～200 μ m,
Fibrous resin combination layer totally is 4～90 volume % with respect to duplexer.
5. duplexer according to claim 1 and 2 is characterized in that,
Per 1 layer thickness of glass-based flaggy is 30～200 μ m.
6. duplexer according to claim 1 and 2 is characterized in that,
Described fiber base material for weave cotton cloth, adhesive-bonded fabric, rove, chopped strand mat or face felt.
7. plywood, it comprises fibrous resin cured matter layer more than 1 layer and the glass-based flaggy more than 1 layer, described fibrous resin cured matter layer is for containing the solidfied material of the prepreg that is soaked with heat-curing resin on fiber base material, described glass-based flaggy is 10～70 volume % with respect to described plywood integral body.
8. plywood according to claim 7 is characterized in that,
The width of described plywood is 10mm～1000mm, and length is 10mm～3000mm, and thickness is 35 μ m～20mm.
9. according to claim 7 or 8 described plywoods, it is characterized in that,
The thickness of described fibrous resin cured matter layer is 3～200 μ m.
10. according to claim 7 or 8 described plywoods, it is characterized in that,
The thickness of described glass-based flaggy is 30～200 μ m.
11. according to claim 7 or 8 described plywoods, it is characterized in that,
Described fiber base material for weave cotton cloth, adhesive-bonded fabric, rove, chopped strand mat or face felt.
12. a multilayer laminate, it comprises a plurality of plywoods, and wherein, at least one plywood is any described plywood in the claim 7～11.
13. a printing distributing board, it has any described plywood and the lip-deep distribution that is arranged on described plywood in the claim 7～11.
14. a printing distributing board, the lip-deep distribution that it has the described multilayer laminate of claim 12 and is arranged on described multilayer laminate.
CN2012204885689U 2011-09-22 2012-09-21 Laminate, laminated board, multilayer laminated board and printed wiring board Expired - Lifetime CN203093220U (en)

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