Composite sheet, its production method, resin multilayer substrate, and its production method
10568216 ยท 2020-02-18
Assignee
Inventors
Cpc classification
H05K1/0353
ELECTRICITY
B32B2255/10
PERFORMING OPERATIONS; TRANSPORTING
B32B3/14
PERFORMING OPERATIONS; TRANSPORTING
B32B27/28
PERFORMING OPERATIONS; TRANSPORTING
B32B27/16
PERFORMING OPERATIONS; TRANSPORTING
H05K3/4632
ELECTRICITY
B32B3/08
PERFORMING OPERATIONS; TRANSPORTING
H05K3/022
ELECTRICITY
B32B3/10
PERFORMING OPERATIONS; TRANSPORTING
B32B27/286
PERFORMING OPERATIONS; TRANSPORTING
B32B27/00
PERFORMING OPERATIONS; TRANSPORTING
B32B15/20
PERFORMING OPERATIONS; TRANSPORTING
International classification
B05D3/00
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A composite sheet includes a resin layer including a liquid crystal polymer as a main material and a first surface and a second surface facing away from each other, a conductor foil disposed on the first surface, and a powder layer including a powder of a liquid crystal polymer as a major component and located on an entirety of the second surface.
Claims
1. A composite sheet comprising: a resin film including a liquid crystal polymer as a main material and a first surface and a second surface facing away from each other; a conductor film disposed on the first surface; and a powder layer including a powder of a liquid crystal polymer as a main material and located on an entirety of the second surface.
2. The composite sheet according to claim 1, wherein at least one of the second surface and the powder included in the powder layer is made of at least one of an ultraviolet ray exposed material, a plasma treated material, and a corona discharged material.
3. The composite sheet according to claim 1, wherein at least a portion of the powder included in the powder layer is fibrillated powder.
4. The composite sheet according to claim 1, wherein at least a portion of the powder included in the powder layer is made of a crushed biaxially oriented liquid crystal polymer sheet material.
5. A resin multilayer substrate comprising: a stack of composite sheets; wherein each of the composite sheets includes: a resin film including a liquid crystal polymer as a main material and a first surface and a second surface facing away from each other; a conductor film disposed on the first surface; and a powder layer including a powder of a liquid crystal polymer as a main material and located on an entirety of the second surface.
6. The resin multilayer substrate according to claim 5, wherein at least one of the second surface and the powder included in the powder layer is made of a least one of an ultraviolet ray exposed material, a plasma treated material, and a corona discharged material.
7. The resin multilayer substrate according to claim 5, wherein at least a portion of the powder included in the powder layer is fibrillated powder.
8. The resin multilayer substrate according to claim 5, wherein at least a portion of the powder included in the powder layer is made of a crushed biaxially oriented liquid crystal polymer sheet material.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
First Preferred Embodiment
(27) With reference to
(28) Before specifically describing the method for producing the composite sheet according to the present preferred embodiment, the powder of the liquid crystal polymer (hereinafter also referred to as LCP) used with this production method will first be described. This is because when performing the method for producing the composite sheet according to the present preferred embodiment, it is preferable to previously prepare a paste in which a powder of an LCP is dispersed.
(29)
(30) Whether LCP powder 61 may undergo the surface treatment or not, as shown in
(31) Preferably, at least a portion of the LCP powder included in paste 67 is fibrillated. Thus, fibrils tangled together or interacting with each other enhance a coating in strength after paste 67 is dried, and thus prevent the LCP powder from easily coming off. An example of the fibrillated LCP powder is shown in
(32) Fibrillated LCP powder includes fibrillated LCP particles. A fibrillated LCP particle is a particle which includes a liquid crystal polymer including a large number of fibrils (e.g., fibrillary fibrous branches, a networked structure composed of fibrils, etc.), and refers to a particle entirely, substantially fibrillated. In other words, it excludes an LCP flake partially having branches of fibrils extending therefrom.
(33) Since the fibrillated LCP powder contains LCP particles having a large number of fibrils, it has a large number of gaps in a vicinity of a surface thereof and will thus have a low bulk density. The fibrillated LCP powder as a whole has a bulk density preferably of about 0.01 to about 0.2, more preferably about 0.03 to about 0.08, for example.
(34) In order to further enhance bondability of the LCP particles and bondability of the LCP particles and the LCP sheet, the fibrillated LCP powder may at least partially undergo a surface treatment by exposure to ultraviolet (UV) rays or a plasma, similarly as done for LCP powder 61. Note that a surface treatment by ultraviolet rays is more preferable than that by a plasma since the former more effectively enhances bondability.
(35) The fibrillated LCP powder can be obtained by the method described in International Publication WO2014/188830, for example.
(36) Note that preferably, at least a portion of the LCP powder is obtained by crushing a biaxially oriented liquid crystal polymer sheet. By thus using the biaxially oriented liquid crystal polymer sheet, powdery LCP powder, rather than fibrous LCP powder, is able to be easily obtained.
(37) Hereinafter, each step of the method for producing the composite sheet according to the present preferred embodiment will be described more specifically.
(38) Initially, as step S1, a resin sheet 12 with a conductor foil as shown in
(39) Conductor foil 17 preferably is composed of Cu and has a thickness of about 18 m, for example. Conductor foil 17 covers one surface of resin layer 2. Conductor foil 17 preferably has a surface with a surface roughness Rz of about 3 m, for example. At a surface of resin layer 2 opposite to the surface thereof on which conductor foil 17 is formed, resin layer 2 has a surface exposed, and this surface preferably has a surface roughness Rz of about 1 m to about 2 m, for example.
(40) Note that a material of conductor foil 17 may be Ag, Al, SUS, Ni, and Au other than Cu, and it may be an alloy of two or more different metals selected from of these metals. Conductor foil 17 is a conductor film. While according to the present preferred embodiment conductor foil 17 has a thickness of about 18 m, conductor foil 17 may have a thickness of about 2 m or more and about 50 m or less, for example. Conductor foil 17 preferably has a thickness allowing a circuit to be provided.
(41) Resin sheet 12 with the conductor foil corresponds to the resin film as referred to in step S1. More specifically, resin sheet 12 with the conductor foil is a resin film which includes a liquid crystal polymer as a main material, a first surface 2a and a second surface 2b facing away from each other, and a conductor foil 17 disposed on first surface 2a as a conductor film.
(42) Note that at this point in time, second surface 2b may undergo the surface treatment, as shown in
(43) Thus, it is preferable that step S3 of applying is preceded by a step S2 of subjecting at least one of second surface 2b and the LCP powder to at least one of ultraviolet ray exposure, a plasma treatment, and a corona discharge treatment.
(44) As step S3, the paste in which the LCP powder is dispersed is applied to the entirety of second surface 2b of resin layer 2, i.e., the resin film. The paste in which the LCP powder is dispersed is paste 67 shown in
(45) As step S4, paste 67 applied to second surface 2b, i.e., paste layer 3, is dried. Thus, as shown in
(46) The method for producing a composite sheet according to the present preferred embodiment provides a composite sheet that reduces an amount of variation of a position of a conductive pattern attributed to a flow of resin during thermocompression bonding. This composite sheet will specifically be described later.
Second Preferred Embodiment
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(48) Composite sheet 101 includes resin layer 2 defining and functioning as a resin film which includes an LCP as a main material and first surface 2a and second surface 2b facing away from each other; conductor foil 17 disposed on first surface 2a and defining and functioning as a conductor film; and powder layer 4 including an LCP powder as a main material and located on the entirety of second surface 2b.
(49) The composite sheet according to the present preferred embodiment includes powder layer 4 on a surface thereof opposite to that on which the conductor film is located, and reduces an amount of variation of a position of a conductive pattern attributed to a flow of resin during stacking and thermocompression bonding. The ground thereof will be described with reference to
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(51) Both are stacked one on the other, as shown in
(52) Finally, a portion of powder layers 4 that is sandwiched by the upper and lower composite sheets is compressed as it is sandwiched, as shown in
(53) As has already been set forth in describing the production method, it is preferable that at least one of second surface 2b and the powder included in powder layer 4 undergoes at least one of ultraviolet ray exposure, a plasma treatment, and a corona discharge treatment, since by adopting this configuration, at least one of second surface 2b and the powder is surface-modified, and adhesive strength (or bonding strength) after compression and heating is enhanced and the resin multilayer substrate is increased in reliability. It is more preferable that both second surface 2b and the powder included in powder layer 4 undergo such a surface treatment.
(54) Preferably, at least a portion of the LCP powder included in powder layer 4 is fibrillated, since by adopting this configuration, powder layer 4 is further enhanced in adhesion strength. Furthermore, as has been discussed above, the fibrillated LCP powder has a low bulk density. Accordingly, in a case in which even if powder layer 4 has some thickness it includes the fibrillated LCP powder, a portion of powder layer 4 that overlaps conductive pattern 7 easily moves to a side to avoid conductive pattern 7.
(55) At least a portion of the LCP powder included in powder layer 4 is obtained by crushing a biaxially oriented LCP sheet, since by adopting this configuration, a powdery LCP powder, rather than a fibrous LCP powder, is able to be easily obtained.
Third Preferred Embodiment
(56) With reference to
(57) The method for producing the resin multilayer substrate includes a step S11 of preparing a plurality of composite sheets; a step S12 of forming a stack by stacking a resin sheet group at least including the prepared plurality of composite sheets and each containing a liquid crystal polymer as a main material; and a step S13 of compressing and heating the stack to integrate the stack, the plurality of composite sheets each including a resin film which includes a liquid crystal polymer as a main material and a first surface and a second surface facing away from each other; a conductor film disposed on the first surface; and a powder layer including a powder of a liquid crystal polymer as a main material and provided on the entirety of the second surface. In step S12 of stacking, the conductor film has at least a portion overlapping the powder layer.
(58) As step S11, two or more composite sheets 101 as shown in
(59) Subsequently, as shown in
(60) Subsequently, etching is done with resist pattern 13 used as a mask to remove a portion of conductor foil 17 that is not covered with resist pattern 13, as shown in
(61) Subsequently, as shown in
(62) While the filling conductive paste may contain copper, tin or the like as a major component, it may instead contain silver as a major component, for example. Preferably, the conductive paste contains in an appropriate amount such a powdery metal that forms an alloy layer with a metal which is a material of conductive pattern 7 at a temperature applied subsequently when stacked resin layers undergo thermocompression bonding (hereinafter referred to as a thermocompression bonding temperature). Since this conductive paste contains copper, or Cu, as a major component to exhibit conductance, it is preferable that this conductive paste include at least one type of Ag, Cu and Ni and at least one type of Sn, Bi and Zn other than the major component. Thus, by introducing the conductive paste, a conductor via 6 is formed.
(63) Note that while in the above example via hole 11 is initially formed followed by forming conductive pattern 7 followed by forming conductor via 6, this order is not exclusive. For example, conductive pattern 7 may initially be formed followed by forming via hole 11 followed by forming conductor via 6.
(64) Subsequently, as step S12, as shown in
(65) Note that, in the example shown in
(66) As step S13, by compressing and heating stack 1 to integrate it, as shown in
(67) The method for producing a resin multilayer substrate according to the present preferred embodiment reduces an amount of variation of a position of a conductive pattern attributed to a flow of resin during thermocompression bonding, and produces a resin multilayer substrate with precision.
(68) Preferably, the method for producing a resin multilayer substrate according to the present preferred embodiment is performed such that, in step S12 of stacking to form a stack or step S13 of integrating, a portion of powder layer 4 that overlaps conductive pattern 7 defining and functioning as a conductor film at least partially moves to a side to avoid conductive pattern 7, since this allows powder layer 4 and conductive pattern 7 to have a uniform total thickness to significantly reduce or prevent displacement of conductive pattern 7.
(69) In the method for producing a resin multilayer substrate according to the present preferred embodiment, preferably, at least a portion of the LCP powder included in powder layer 4 is fibrillated, since this enhances adhesion thereof to resin layer 2 composed mainly of the LCP. As has been discussed above, it is preferable that, as the LCP powder included in powder layer 4, a fibrillated LCP powder be at least partially included. Furthermore, it is particularly preferable that the fibrillated LCP powder be mixed with a non-fibrillated LCP powder, as appropriate, and thus used.
(70) In the method for producing a resin multilayer substrate according to the present preferred embodiment, preferably, at least a portion of the LCP powder included in powder layer 4 is obtained by crushing a biaxially oriented LCP sheet, since by thus using the biaxially oriented LCP sheet, an LCP powder of a good quality is able to be obtained.
Fourth Preferred Embodiment
(71) With reference to
(72) Resin multilayer substrate 201 according to the present preferred embodiment produced using a composite sheet having been described in the previous preferred embodiments reduce an amount of variation of a position of a conductive pattern attributed to a flow of resin during thermocompression bonding. Accordingly, a significantly reliable resin multilayer substrate can be produced.
Exemplary Experiment
(73) In order to verify advantageous effects of preferred embodiments of the present invention, a non-limiting experiment conducted by the inventors will be described. A 125-m-thick, biaxially stretched LCP film was used as a raw material for a fibrillated LCP powder. This film was primarily crushed using a rotary cutter mill. In the primary crushing, only what was crushed to pass through a sieve having a diameter of 3 mm was collected. The primarily crushed film was further, secondarily crushed using a freezing and crushing machine to obtain an LCP powder.
(74) The obtained LCP powder has a passage rate (in weight) of 22% for a 40 m mesh, a passage rate (in weight) of 67% for a 106 m mesh, and a passage rate of 90% for a 150 m mesh.
(75) Subsequently, the LCP powder sieved through the 150 m mesh was used and fibrillated using a high pressure wet shredding apparatus. As a dispersion medium, a 20% aqueous solution of ethanol was used, and the LCP powder was added at a weight ratio 5%. The high pressure wet shredding apparatus has a nozzle which is a cross type nozzle having a diameter of 250 m, and passing through the nozzle was done 10 times with a pressure of 200 MPa applied. The obtained dispersion liquid was further diluted with a 20% aqueous ethanol solution to have a solid content with a weight ratio of 2% and underwent an ultraviolet ray treatment in a method described in International Publication WO2014/109199, and thereafter was dried with a spray dryer to obtain a fibrillated powder in the form of a powdery matter.
(76) This powdery matter was added to butanediol (viscosity: about 90 mPa.Math.s) at a weight ratio of 8% and furthermore, the LCP powder obtained by freezing and crushing that was sieved through the 40 m mesh, and then underwent an ultraviolet ray treatment in a method described in International Publication WO 2014/109199, was added at a weight ratio of 8%, and the intermediate product was agitated to obtain a pasty matter. The obtained pasty matter had a viscosity of about 10000 mPa.Math.s. This pasty matter was allowed to stand for 1 day, and there was no solid content observed sedimented.
(77) An LCP base material having a thickness of 18 m with a 18-m-thick copper foil stuck thereon had a surface thereof opposite to the copper foil subjected to an ultraviolet ray treatment to have bondability, and subsequently, the above described pasty matter was applied by screen printing (70 screen meshes/inch (about 27.6 meshes/cm), and an aperture of 263 m) to provide a coating. Subsequently, the coating was dried on a hot plate at 250 C. for 5 minutes. Thus, an LCP base material sheet (a composite sheet) with a coating composed of a mixture of fibrillated LCP powder and non-fibrillated LCP powder and having a thickness of about 30 m was obtained. The obtained coating had a sufficient strength and a sufficient adhesiveness to a substrate so that it does not peel or come off when forming an interconnect by a subtractive method.
(78) As a sample 1, on the copper foil of the LCP base material sheet with the above described coating provided thereon, an interconnect of L/S=50/25 was formed in the subtractive method, and six such sheets were stacked, and compressed and heated to produce a resin multilayer substrate. This resin multilayer substrate is structured such that by the copper foil a conductive pattern imitating a circuit is disposed inside. In the heating and compressing step, a vacuum press apparatus was used to perform a press at 280 C. and 4 MPa for 5 minutes. The obtained resin multilayer substrate's cross-sectional photographic image is shown in
(79) As a comparative example 1, an LCP base material sheet which did not have the above described coating on a surface thereof opposite to the copper foil was used to form a resin multilayer substrate in a similar method. The obtained resin multilayer substrate's cross-sectional photographic image is shown in
(80) In the comparative example a portion of an internal conductive pattern was significantly displaced and arranged in a disturbed manner, whereas in sample 1 the internal conductive pattern's arrangement had only a small disturbance. From this, it has been confirmed that preferred embodiments of the present invention achieve advantageous effects.
(81) While preferred embodiments of the present invention have been described above, it is to be understood that variations and modifications will be apparent to those skilled in the art without departing from the scope and spirit of the present invention. The scope of the present invention, therefore, is to be determined solely by the following claims.