CN1158101A - Foiled UD-prepreg and PWB laminate prepared therefrom - Google Patents

Foiled UD-prepreg and PWB laminate prepared therefrom Download PDF

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Publication number
CN1158101A
CN1158101A CN95195145A CN95195145A CN1158101A CN 1158101 A CN1158101 A CN 1158101A CN 95195145 A CN95195145 A CN 95195145A CN 95195145 A CN95195145 A CN 95195145A CN 1158101 A CN1158101 A CN 1158101A
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China
Prior art keywords
layer
laminate
prepreg
semi
pwb
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CN95195145A
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Chinese (zh)
Inventor
E·米德尔曼
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AMP-AKZO LINLAM VOF
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AMP-AKZO LINLAM VOF
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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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/08—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers
    • B29C70/088—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers and with one or more layers of non-plastics material or non-specified material, e.g. supports
    • 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
    • B32B15/04—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
    • B32B15/095—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 comprising polyurethanes
    • 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
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • 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
    • 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
    • B32B5/12—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 characterised by the relative arrangement of fibres or filaments of different layers, e.g. the fibres or filaments being parallel or perpendicular to each other
    • 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
    • B32B5/18—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 features of a layer of foamed material
    • 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
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
    • B29K2105/10—Cords, strands or rovings, e.g. oriented cords, strands or rovings
    • B29K2105/101—Oriented
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
    • B29K2105/10—Cords, strands or rovings, e.g. oriented cords, strands or rovings
    • B29K2105/101—Oriented
    • B29K2105/108—Oriented arranged in parallel planes and crossing at substantial angles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/24—Condition, form or state of moulded material or of the material to be shaped crosslinked or vulcanised
    • B29K2105/243—Partially cured
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/25—Solid
    • B29K2105/253—Preform
    • B29K2105/256—Sheets, plates, blanks or films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2705/00—Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0276—Polyester fibres
    • B32B2262/0284—Polyethylene terephthalate [PET] or polybutylene terephthalate [PBT]
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • 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
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/12—Copper
    • 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
    • B32B2363/00—Epoxy resins
    • 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
    • H05K2201/0287—Unidirectional or parallel fibers

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

The invention relates to a substrate material for manufacturing PWB laminated boards. The laminated board is a foiled UD-half-solidified prepreg, which comprises a layer of conductive metal foil and a layer of tiered reinforcing fibers. With the diameter less than 30 um, the reinforcing fibers which are soaked by matrix resin which is not completely solidified are parallel and in a single direction. The two layers are felted together. The foiled UD-half-solidified prepreg can be used for manufacturing UD-cross cord fabric PWB laminated boards through the following method: The foiled UD-half-solidified prepreg and other UD layers are stacked and pressed together, while the UD layers are sandwiched. The UD layers can be non-foiled UD half-solidified prepregs or UD composite layers of illiquidity.

Description

Foliation list orientation prepreg reaches by its PWB laminate of making
The present invention relates to a kind of substrate plate that is used to make the PWB laminate, said PWB laminate comprises one deck at least and is soaked into the fortifying fibre of parallel and single-orientated (UD), just a kind of UD semi-solid preparation layer by not completely crued matrix resin as yet.The invention still further relates to by this UD semi-solid preparation layer and make, be used for the laminate of printed substrate (PWB).
There is a kind of UD prepreg material that is used to make PWB to be disclosed in US 4,814, on 945.Its disclosure relates to a kind of PWB laminate that contains the matrix resin that strengthens with parallel aramid fibre.This laminate is stacked in another above layer and constitute by the aromatic polyamides strip of the single orientation of multilayer by mode one lamination of right-angled intersection.The preparation method of this aromatic polyamides strip is arranged in parallel the individual layer aramid fibre to form a kind of fiber band, then with this fiber band of resin-coating and with the heating of said resin so that its reach a kind of semi-solid preparation or " B "-stage (state of " B "-Stage).
A deorientation that problem is the UD layer that when preparation UD cross-ply pressing plate, causes easily.Just must keep suitable orientation in order to obtain a kind of laminate, and said flatness is the performance of a particular importance of PWB laminate with enough flatnesses.But if particularly use the matrix resin that still is in flow regime, the material in B-stage for example, the just very possible danger that disorientation takes place, this is because the mobile tension force that causes controlling suitably material appears in material in lamination process, and therefore causes the orientation of UD layer suitably not control.
In addition, people wish to make the cross-ply composite laminate that a kind of UD-strengthens on the basis of prepreg.Being used for prepreg (being generally braided glass fibre fabric prepreg) serves as that the basic technology of making laminate is the routine techniques in PWB laminate field, and its advantage is can use resin system and be proved to be the lamination with durability in this field.Certainly, because the advantage of woven fibre structure makes conventional prepreg be difficult for producing the problem of disorientation.Yet, use a kind of UD-cross-ply structure to replace knitted fabric structure can bring tangible advantage, for example to the improvement of surface quality and have lower thermal linear expansion coefficient (TCE) in the x and y direction, can bring the fiber of high level and the better optimization of dimensional stability.Owing to these reasons, make UD-cross-ply pressing plate extremely be suitable as the PWB substrate.Certainly, have only when the method that is used to make these laminates can keep suitable orientation and could obtain said advantage.
It is known in the prior art that certain methods is wherein arranged, for example can be from EP 478051, WO 92/22191 and US 4,943, and 334 learn.But do not have a kind of method to be based on prepreg lamination technology in these methods, therefore the invention still further relates to provides a kind of UD cross-ply pressing plate based on the UD prepreg.
In DE 3542295, pointed out emphatically one with the relevant problem of UD fiber orientation.This patent document relates to a kind of light shielding material based on the basalis that contains orientation fibers in the matrix resin.A wherein disclosed fact is, by the position deviation of parallel fibers when applying the synthetic paper tinsel of one deck heat-shrinkable on the basalis and can eliminate in extrusion forming.Use the heat-shrinkable paper tinsel will cause that slight bending takes place the UD prepreg on machine direction.Though this situation may meet the requirements under the situation of shielding material, under the situation of PWB laminate, but must avoid fully.
Another problem that causes probably when utilizing the UD prepreg is, prepare thin laminate if desired, the so this quilt still individual layer UD fiber of flowable resin impregnated will be unmanageable (even this resin is that solid state also is like this in processing temperature).Because the UD layer is torn in the vertical easily, thereby makes the problems referred to above even more serious.This is because the intensity low cause of UD layer on the direction vertical with said fiber.
When being a kind of thermosetting resin, said not completely crued as yet matrix resin also can run into another problem.Opposite with thermoplastic resin, this not completely crued as yet thermosetting resin does not also have its final properties, and just all mechanical performances remain inferior.Because this prepreg damages easily, therefore adding the problem that may cause other man-hour.
Should be noted that other relate to the goods that are shaped to a kind of circle about background technologies of using the UD prepreg, for example golf club handle etc.JP-puts down-4-329, and 132 disclose a kind of compound prepreg goods that are used for this purpose.This compound prepreg contains two kinds of different parallel fibers and a layer thickness is the metal level of 5-100 μ m, and in said two kinds of different fibers, coarse-fibred diameter is 30-500 μ m, and the diameter of fine fibre is 5-30 μ m.
Should meet the modern PWB product that requires for those, the very important point is that any fortifying fibre all should be that a kind of diameter is less than 30 μ m, be preferably the long filament of 3-15 μ m, because, must ban use of thicker fiber in order to obtain satisfied boring and desirable surface flatness.Particularly, will produce processing problems for thin prepreg with tiny fortifying fibre.
Other similar background technologies are that JP-puts down-6-008 240.This patent documentation discloses a kind of structural composite material, and its outmost surface layer is covered by layer of metal or metal compound film.The core body of this compound can be strengthened by a kind of parallel and single-orientated yarn, and its skin is strengthened by glass cloth.The disclosure content relates in type, circular goods, for example golf club handle or antenna etc.
Japanese Patent Application Publication No.201 699/1985 discloses a kind of heat bondable electrical shielding material, this electrical shielding material comprises a metal forming, thermal bondable resin bed that forms on this metal forming and the many parallel enhancing wire that is fixed in this resin bed.The diameter of these conductive wires is 0.03～0.5mm, and their mutual spacings are 10～15cm.The document also discloses that, produce gauffer if prevent this metal forming, then said shielding material must with a kind of padded coaming, for example polyurethane foam sheet is intertwined.
Another background technology about the PWB laminate comprises EP 0 372 505.In fact the document discloses a kind of fibre-reinforced thermoplastic laminates.This fiber reinforcement effect can be any form.This thermoplastic laminates has the metal forming that one deck sticks in the above when resin is in molten condition.Said resin is normally a kind of to be that thermoplasticity then is solid-state material when high temperature when room temperature.Disclosed this laminate is not to resemble the base material that is used to make PWB the purpose product of the present invention, because itself just uses as the PWB laminate.Therefore, the laminate of making according to EP 372505 is the laminate of the final performance of a kind of PWB of having substrate.Real purpose of the present invention is a kind of UD prepreg that can be used for making PWB, but they itself and be not suitable as the PWB laminate and use.Because very thin, and only on single direction, have the fiber reinforcement effect, so it will only have suitable performance on this direction.Therefore it is unmanageable and tears easily.As mentioned above, a kind of as yet not during completely crued thermosetting resin when using, the problems referred to above are more obvious.
The objective of the invention is to provide a kind of like this UD semi-solid preparation layer, this semi-solid preparation layer allows further processing, and can not cause aforesaid problem, and it is itself to be applicable to the type of making the PWB laminate basically.And then another object of the present invention is that a kind of like this UD semi-solid preparation layer will be provided, and this semi-solid preparation layer allows to use a kind of not completely crued as yet thermosetting resin and can not cause and above-mentioned relevant other problems.
For this purpose, the invention provides a kind of base material that is used to make the PWB laminate, this PWB laminate comprises one deck UD semi-solid preparation layer of type as mentioned above, the diameter of the fortifying fibre in this semi-solid preparation layer is below 30 μ m, and the metal forming that comprises one deck conduction, Copper Foil for example, this conductive metal foil is adhered on the said UD semi-solid preparation layer.
This conductive metal foil layer can make UD semi-solid preparation material have enough intensity on the direction perpendicular to fiber, thereby can prevent from adding tearing of causing man-hour.If with layer of metal paper tinsel lamination in the above earlier, so a kind of processing problems of thin copper foil has also just solved before the UD prepreg is cut into required size.
As mentioned above, the present invention relates to a kind of base material that is used to make the PWB laminate.This base material comprises a kind of layer structure that is bonded together mutually by adjacent two layers, and it comprises the layer of metal paper tinsel, and for example Copper Foil, and one deck is soaked into by not completely crued matrix resin as yet, parallel and single-orientated fibrage.
Term " prepreg " is being well-known in the art, it typically refer to a kind of with resin impregnated reinforcing material and itself be to solidify (partly).It still is in a kind of stage of being clamminess usually.Term " not completely crued as yet host material " is meant that this resin can also further solidify.Under the situation of thermosetting resin, it typically refers to the matrix resin that is in the B stage.Some host material (matrix resin) stage is being meant " A ", " B " and " C " stage usually in the art, and the A stage is meant that uncured resin is (just under the situation of thermosetting resin; Be in the uncured stage); The B stage typically refers to the partly solidified stage (under the situation of thermosetting resin: this reaction proceeds to the longer strand of formation, but does not form complete net as yet), and the C stage is meant the completely crued stage.Term A stage, B stage and C stage all are well-known for the person of ordinary skill of the art, do not need to be further explained herein.
Foliation prepreg of the present invention can be pressed together layer by layer with other semi-solid preparation layers or curing materials.Certainly, said other stratiform things also can contain the braiding fortifying fibre, but, if wish to keep fully the advantage of UD humidification, said other layers preferably should have the UD parallel fibers, that is to say that it should be a UD semi-solid preparation layer or such as disclosed curing in WO 92/22191 (can not flow) UD composite bed.
The standard base material that is used to make printed substrate at present usually can be according to for example at C.F, Coombs, Jr. the method manufacturing that printed circuit handbook (Printed Circuits Handbook) is described in (McGraw-Hill), this method comprise the following steps:-with the solution impregnation braided glass fibre of a kind of epoxy resin in MEK.-then, solvent is evaporated and allow resin partly be cured to a kind of so-called B-stage.-prepreg that is obtained cut into suitable size and with its long-pending stacking between two Copper Foils.-pressurize under the temperature that improves with a multidaylight press, this assembly is solidified.-by etching the laminate that is coated with Copper Foil in its two sides that makes by this method is made printed substrate then.
PWB laminate based on UD prepreg of the present invention can be by similar methods manufacturing basically.Certainly, the preparation method of UD semi-solid preparation base material is different from the method for dipping and curing braided fiber.The UD prepreg can be made usually as follows, just be coated on the Copper Foil to form a kind of resin bed of foliation with matrix resin, heat the flowability of resin bed to guarantee that this resin has is enough to soak into filament fiber of this foliation, then the parallel filaments fiber is attached on the resin to form a kind of foliation UD-fortified resin layer.This soaks into step and also can be undertaken by opposite program, just earlier the parallel filaments fiber is attached on the resin bed that not have enough flowabilities, and heating this resin bed then so that it has is enough to soak into filametntary flowability.Dissimilar according to resin, the UD-of this foliation is strengthened resin bed, perhaps further heating, perhaps accept the photochemistry irradiation, so that this resin partly solidifies (for example arriving the B-stage), perhaps with its cooling so that this resin solidification (for example when using a kind of thermoplastic resin that at room temperature solidifies).Find that unexpectedly the foliation UD prepreg that is obtained is than exposed Copper Foil and corresponding not the two all easier processing of UD prepreg of foliation.The prepreg of this foliation is cut into suitable size, and the long-pending superimposition of UD stratiform thing of foliation is not laminated together with itself and other then.The UD layer of foliation will not form internal layer, it is clamped between the UD prepreg (copper foil layer is on the outer surface) of two foliations and forms a kind of sandwich of layers.
In this respect, the invention still further relates to a kind of manufacture method of PWB laminate, in said laminate, several layers is included in the resinous substrates, and the stratiform thing of parallel and single-orientated fortifying fibre is folded and pressed together by long-pending.In the method, make a kind ofly to paste on the UD-semi-solid preparation layer and the foliation UD-semi-solid preparation layer that forms forms the outer surface layer of this laminate, and make this conductive metal foil be in the outside of this laminate by one deck conductive metal foil.In one embodiment, the stratiform thing that is used to form this PWB laminate internal layer is a kind of semi-solid preparation layer, wherein contains by not completely crued matrix resin as yet to soak into parallel and single-orientated fortifying fibre, just a kind of UD prepreg of not foliation.In another embodiment, the stratiform thing that is used to form this laminate internal layer is made of some illiquidity UD-composite layers or illiquidity UD cross-ply pressing plate.
Term " illiquidity UD compound " is meant a kind of composite that contains single-orientated fortifying fibre, and said fortifying fibre has cured in the host material that can not flow again in the following process program between a kind of.Generally speaking, it is meant its storage and adds man-hour, and said illiquidity UD compound is under a kind of condition of the pressure and temperature that is lower than its softening point (promptly being lower than its Tg or apparent Tg), perhaps has been cured to a kind of stage that can not flow again.For the ease of storing and processing, preferably the curing with illiquidity UD compound proceeds to the C stage, perhaps use those resins that contains the rigid molecule chain, just it has reached one and still has been called the B stage, but normal store and processing conditions under belong to stage of first valve state.Yet when the pressurization to laminated area is when carrying out under isobaric condition, the material that is in the A stage also can use clearly.
Formed in the embodiment of internal layer by illiquidity UD compound a kind of, these stratiform things can be according to the method preparation of WO 92/22191.It also can utilize a kind of for example disclosed in WO92/22192, apply or the intermediate base of uncoated adhesive at the bottom of and long-pending folded and laminated together with foliation UD prepreg of the present invention.
Known already, UD cross-ply pressing plate preferably balance with symmetry.Term " balance " is meant to have equal performance (filament fiber that for example has equal amount on x and y both direction) on the orthogonal both direction, term " symmetry " is meant on the whole thickness of laminate to have the minute surface symmetry, that is to say that this laminate is the central plane symmetry.The plane of symmetry or the boundary face of two-layer UD layer or the imagination plane of extending by one deck UD layer of this laminate outer surface extended and is parallel at center by this laminate, and this depends on the number and the order of UD layer in the whole thickness of laminate.This have a right-angled intersection UD enhancement layer, and the major advantage of the laminate of balance and central plane symmetry is it on x and y both direction (i.e. two orthogonal machine directions) have identical performance.
Particularly preferably be this laminate and have formation as described below, just the UD-enhancement layer is orientated according to the mode of one of following pattern defined, they are repeated on given orientation with the orientation of 0 ° and 90 ° form right angle quadrature and the relative thickness according to the rules of each layer in structure always, and these orientations must be 0 °/90 ° 90 °/0 °; 0 °/90 ° 90 °/0 ° 0 °/90 ° 90 °/0 °.
In general, in order to be applied among the PWB, the thickness that the UD-enhancement layer in laminate of the present invention is every layer is in the scope of 6～800 μ m, preferably in the scope of about 12.5～400 μ m.
The appearance of cross-ply pressing plate is two-layer by foliation UD prepreg of the present invention, and promptly a kind of stratiform thing with layer of metal paper tinsel (for example Cu) and one deck UD layer (for example 0 °) constitutes.In above-mentioned example, internal layer UD layer has the thickness that doubles outer UD layer, and this internal layer can be made of a UD prepreg.Certainly, may produce the danger of above-mentioned disorientation in the case, but the UD layer of double thickness can not cause the processing problems (this problem can solve by the method for pasting metal forming according to the present invention) that resembles the thickness in monolayer UD layer.In this embodiment, preferably this laminating operation carries out under isobaric condition, causes mobile motive force to avoid producing.But the illiquidity UD composite bed that meets WO 92/22191 of preferred inner each layer for stipulating above.
From above can clearly be seen that, the long-pending folded mode of (copper foil layer is in outer surface) makes the regulation of a kind of pattern in the above-mentioned pattern of oriented of UD-enhancement layer between the preferably this UD prepreg that is clamped in two foliations by the UD layer of foliation not, promptly Cu0 °/90 ° 90 °/0 ° Cu or Cu0 °/90 ° 90 °/0 ° 0 °/90 ° 90 °/0 ° Cu.
Laminating operation can carry out in multidaylight press, autoclave, vacuum press, biobelt press or any other suitable device.
The PWB laminate of making on the basis of foliation UD-prepreg of the present invention is applicable to multilayer PWB (MLB), for example disclosed product in WO 92/22192.
The material that is used for the present invention does not have strict especially requirement.The preferred material of hereinafter discussing that uses.
Host material can be thermoplasticity or heat cured polymer, preferably thermosetting resin.Be more preferably the host material of use, but other resins can use also on principle based on epoxy resin.Example comprises: cyanate, unsaturated polyester (UP) (UP) resin, vinyl ester resin, acrylate, BT epoxy resin, bimaleimide resin (BMI), polyimides (PI), phenol resin, triazine, polyurethane, silicone resin, two citraconic acid resin (BCI).In addition, also said resin combination can be used, and also can be with above-mentioned resin and some thermoplastic that is fit to, for example PPO, PES, PSU and PEI etc. mix uses.Having interpenetrating polymer networks (IPN) also is fit to use.Preferably with some compounds, the compound of for example phosphorous or halogen-containing (particularly brominated), fusion is advanced in the host material to give anti-flammability.Particularly preferably be a kind of 100 weight portion Epikote that have an appointment that contain 828EL, about 73 weight portion Epikote 5050 and the host material of the complex of about 4 weight portion boron trifluorides and monoethyl amine, because this host material has good flowing property and curing performance.
Though preferred reinforcing material is made up of filament yarn, discontinuous fiber also can use.According to the present invention, this strengthens silk preferably from following thing group selection: glass fiber is E-glass fiber, A-glass fiber, C-glass fiber, D-glass fiber, AR-glass fiber, R-glass fiber, S1-glass fiber and S2-glass fiber for example; And various ceramic materials, for example aluminium oxide and carborundum.That be fit to use also has material based on the fiber, particularly so-called liquid crystal polymer of polymer, for example: to phenylene terephthalate amine (PPDT), poly-benzo-dioxazole (PBO), polyphenyl and double thiazole (PBT) and polybenzimidazoles (PBI); And those based on poly-ethylidene naphthalate (PEN) (naphthalate), the fiber of PETG (PET) and polyphenylene sulfide (PPS).The diameter of these fibers (long filament) should for example can be 20 μ m less than 30 μ m.Usually the more concrete scope of its diameter is 3～15 μ m, preferably 5～13 μ m.
Usually the fiber content in matrix is about 10～90vol%, preferably in about scope of 40 to about 70vol%.With the fiber volume percentage serves as that about 50vol% is the most satisfied.
The situation of the laminate that strengthens with braided fiber is opposite, also is suitable as soft board or flexible laminate and rigidity-flex layer pressing plate by the composite laminate of the inventive method manufacturing.When being used for soft board, yarn fabric ruptures at warp and parallel fiber interface point easily, its reason is, fiber and those fibers perpendicular to bending direction along the bending direction orientation are co-located on fabric, owing to the high fibre density at these interface point places has increased this adverse effect, thereby cause under the situation of relatively low flexibility, just cracking.These crackles make the circuit intersection point (conductive traces) of stress high concentration on flexible laminate locate, and therefore cause the risk of breakage of height, and it will cause opening circuit of circuit.In the flexible laminate soft section of rigidity-flex layer pressing plate (or), the orientation preferred parallel of outer UD layer is in desirable bending direction.
In addition, UD cross-ply pressing plate of the present invention extremely is suitable as the support material of using in the device that has various different integrated circuits (multi-disc module).This mainly gives the credit to favourable thermal coefficient of expansion (TCE), it mainly is because bigger fiber volume percentage causes, when using the laminate of intersection cord, can obtain big fiber volume percentage, and TCE in the case can approach and PWB, especially the TCE of the electronic component that is connected with MLB (chip).This electron-like element can be installed on the surface of MLB (chip is on base plate), perhaps electronic component is embedded in the substrate at the bottom of the such intermediate base of WO for example 92/22192 in (chip is in base plate).
Further explain the laminate sub-assembly that on the basis of foliation UD-prepreg of the present invention, makes below with reference to the accompanying drawings.
Fig. 1 illustrates foliation UD prepreg of the present invention (1).The figure shows the cross sectional view of x and y direction, each symbolic representation in the figure: Copper Foil (2), it is fitted on the UD semi-solid preparation layer (3), this semi-solid preparation layer (3) is made of some parallel and single-orientated fortifying fibres (4), and fortifying fibre (4) quilt not completely crued matrix resin (5) as yet soaks into.
Fig. 2 illustrates a kind of illiquidity UD composite plate (6) according to WO 92/22191.Each symbolic representation in this figure (x and y direction cross section): by UD fiber (7) constitute two-layer, these fibrages are soaked into by the matrix resin of illiquidity (8).
Fig. 3 illustrates a kind of Cu0 °/90 ° 90 °/0 ° Cu PWB laminates being made by the long-pending folded also lamination of illiquidity UD composite plate (6) and two-layer foliation UD prepreg (1).

Claims (7)

1. base material that is used to prepare the PWB laminate, it comprises, and one deck soaks into by the not completely crued as yet matrix resin of many quilts, the UD semi-solid preparation layer that parallel and single-orientated fortifying fibre constitutes, it is characterized in that, this base material is a kind of UD prepreg of foliation, it comprise one deck paste on the UD semi-solid preparation layer conductive metal foil and be in the UD semi-solid preparation layer, diameter is less than the fortifying fibre of 30 μ m.
2. the base material that is used to prepare the PWB laminate as claimed in claim 1 is characterized in that, metal forming wherein is the Copper Foil of a kind of thickness below 18 μ m.
3. the base material that is used to prepare the PWB laminate as claimed in claim 1 or 2 is characterized in that matrix resin wherein is a thermosetting resin.
4. method that is used to prepare UD semi-solid preparation layer, wherein, a kind of not bonding long filament of textile forms is arranged to ground by parallel and folk prescription, it is characterized in that, this parallel filaments is soaked into by a kind of flowable matrix resin, and this matrix resin then is bonded on one deck conductive metal foil and by this metal forming and is supported.
5. PWB laminate, it has conductive metal foil layer that is on its two side external surface and the laminate that is made of many layer UD layers, each layer UD layer all contains the resinous substrates that is strengthened by single-orientated parallel fibers, these UD layers are arranged by the mode of cross-ply, and said laminate has the plane that is parallel to two outer surfaces symmetrically, it is characterized in that conductive metal foil wherein and the outer UD layer that is adjacent are made of each described foliation UD prepreg in the claim 1～3.
6. method that is used to make the PWB laminate, several layers semi-solid preparation layer is wherein folded and is pressed together by long-pending, these semi-solid preparation layers contain by not completely crued matrix resin as yet and soak into, parallel and single-orientated fortifying fibre, it is characterized in that, the semi-solid preparation layer that forms this laminate outer surface is made of a kind of UD prepreg of foliation, and this prepreg contains one deck and pastes conductive metal foil on the UD semi-solid preparation layer, and this conductive metal foil is in the outside of this laminate.
7. method that is used to make the PWB laminate, wherein, contain and be in the resinous substrates, the several layers of parallel and single-orientated fortifying fibre is folded and is pressed together by long-pending, it is characterized in that, each layer that forms this laminate internal layer is made of illiquidity UD composite bed, constitute by a kind of foliation UD prepreg and form the two-layer of this laminate outer surface, said foliation UD prepreg comprises one deck conductive metal foil and one deck and contains by not completely crued matrix resin as yet and soak into, the stratiform thing of parallel and single-orientated fortifying fibre, described conductive metal foil paste on the above-mentioned stratiform thing and are in the outside of this laminate.
CN95195145A 1994-09-19 1995-09-18 Foiled UD-prepreg and PWB laminate prepared therefrom Pending CN1158101A (en)

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