CN116787887A - Multilayer film, metal-clad laminate, and circuit board - Google Patents
Multilayer film, metal-clad laminate, and circuit board Download PDFInfo
- Publication number
- CN116787887A CN116787887A CN202310223489.8A CN202310223489A CN116787887A CN 116787887 A CN116787887 A CN 116787887A CN 202310223489 A CN202310223489 A CN 202310223489A CN 116787887 A CN116787887 A CN 116787887A
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- CN
- China
- Prior art keywords
- layer
- thermoplastic polyimide
- multilayer film
- polyimide layer
- adhesive layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Landscapes
- Laminated Bodies (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention provides a multilayer film,A metal-clad laminate and a circuit board. The multilayer film has an outer layer portion including a plurality of polyimide layers on both sides of an inner layer portion including an adhesive layer, and further improvement in dielectric characteristics is achieved while ensuring dimensional stability. A multilayer film comprising a plurality of polyimide layers and an adhesive layer, the multilayer film satisfying: a) The total thickness of the thermoplastic polyimide layer and the non-thermoplastic polyimide layer laminated on one side of the adhesive layer is in the range of 2 μm to 20 μm; b) The method meets the following conditions: 65 < P P /P AD < 1,550, by P P ＝P P1 +P P2 、P P1 ＝(E' P100 +E' P200 ) Thickness of polyimide layer [ mu ] m]、P P2 ＝(E' P100 +E' P200 ) Thickness of polyimide layer [ mu ] m]、P AD ＝(E' AD100 +E' AD200 ) Thickness of X adhesive layer [ mu ] m]Expressed, E' P100 、E' P200 Is the storage elastic coefficient [ GPa ] of the polyimide layer at 100 ℃ and 200 DEG C]，E' AD100 、E' AD200 Is the storage elastic coefficient [ GPa ] of the adhesive layer at 100 ℃ and 200 DEG C]The method comprises the steps of carrying out a first treatment on the surface of the c) The dielectric loss tangent at 20GHz, as measured by SPDR resonator, is less than 0.0029 as the whole of the multilayer film.
Description
Technical Field
The present invention relates to a multilayer film, a metal-clad laminate, and a circuit board which are effectively used as materials for electronic parts.
Background
In recent years, along with the progress of miniaturization, weight reduction, and space saving of electronic devices, there has been an increasing demand for flexible printed circuit boards (Flexible Printed Circuits, FPC) which are thin and lightweight, have flexibility, and have excellent durability even if repeatedly bent. Since FPC can be mounted in a three-dimensional and high-density manner even in a limited space, its use is expanding in parts such as wiring, cables, connectors, etc. of electronic devices such as Hard Disk Drives (HDD), digital video discs (Digital Video Disk, DVD), smart phones, etc.
In addition to the higher density, the higher performance of the device is advancing, and therefore, it is also necessary to cope with the higher frequency of the transmission signal. When a high-frequency signal is transmitted, if the transmission loss in the transmission path is large, there occurs a problem such as loss of the electric signal or a longer delay time of the signal. In order to cope with the high frequency of the transmission signal, it is proposed to improve the dielectric characteristics by: an adhesive layer having a large thickness ratio is interposed between insulating resin layers of a pair of single-sided metal-clad laminated plates, and thermoplastic polyimide using dimer acid-type diamine (DDA) in which both terminal carboxylic acid groups of dimer acid are substituted with primary aminomethyl groups or amino groups is used as a material of the adhesive layer (patent document 1). Patent document 1 discloses, as a laminated structure of a resin portion, specifically a layer structure of thermoplastic polyimide layer/non-thermoplastic polyimide layer/adhesive layer/thermoplastic polyimide layer/non-thermoplastic polyimide layer/thermoplastic polyimide layer.
In the layer structure as in patent document 1, in order to further improve the dielectric characteristics, it is effective to increase the thickness of the inner layer portion including the adhesive layer excellent in dielectric characteristics and to thin the thickness of the outer layer portion including the thermoplastic polyimide layer/non-thermoplastic polyimide layer/thermoplastic polyimide layer. However, when the thickness of the non-thermoplastic polyimide layer of the outer layer portion is made thin, the thermal expansion coefficient (Coefficient Of Thermal Expansion, CTE) of the outer layer portion is reduced, and the dimensional accuracy is impaired, so that further improvement of the dielectric characteristics is hindered.
[ Prior Art literature ]
[ patent literature ]
Patent document 1 Japanese patent laid-open publication No. 2018-170417
Disclosure of Invention
[ problem to be solved by the invention ]
The purpose of the present invention is to achieve further improvement in dielectric characteristics while ensuring dimensional stability in a multilayer film having an outer layer portion including a plurality of polyimide layers on both sides of an inner layer portion including an adhesive layer.
[ means of solving the problems ]
The present inventors have made an intensive study and as a result, have found that, focusing on the storage elastic coefficients of the inner layer portion and the outer layer portion at a predetermined temperature, by controlling the elastic coefficient parameters derived from these storage elastic coefficients to have a specific relationship, the ratio of the inner layer portion can be increased while ensuring the dimensional stability of the multilayer film, and low dielectric loss tangent can be achieved; in addition, the thermoplastic polyimide layer is gathered into one layer on one side of the outer layer, and the thickness ratio is increased, so that the whole outer layer can be thinned, and the dimensional stability and the adhesion with the metal layer can be ensured; the present invention has been achieved by increasing the relative thickness ratio of the inner layer portion to achieve low dielectric loss tangent of the entire multilayer film, and by reducing the storage modulus of elasticity at high temperature to alleviate the influence of the inner layer portion on dimensional change.
That is, the present invention is a multilayer film comprising a plurality of polyimide layers and an adhesive layer, and has a layer structure of (1) or (2) below:
(1) Thermoplastic polyimide layer/non-thermoplastic polyimide layer/adhesive layer/non-thermoplastic polyimide layer/thermoplastic polyimide layer,
or,
(2) Thermoplastic polyimide layer/non-thermoplastic polyimide layer/adhesive layer/thermoplastic polyimide layer/non-thermoplastic polyimide layer/thermoplastic polyimide layer. The multilayer film of the present invention satisfies the following conditions a) to c):
a) The total thickness of the thermoplastic polyimide layer and the non-thermoplastic polyimide layer laminated on one side of the adhesive layer is in the range of 2 μm to 20 μm;
b) Satisfying the following formula (i);
65＜P P /P AD ＜1,550…(i)
{ here, P P Is the elasticity coefficient parameter of the polyimide layer, P AD The elastic coefficient parameter of the adhesive layer is represented by the following formulas (ii) to (v):
P P ＝P P1 +P P2 …(ii)
P P1 ＝(E' P100 +E' P200 )×t p1 …(iii)
P P2 ＝(E' P100 +E' P200 )×t p2 …(iv)
P AD ＝(E' AD100 +E' AD200 )×tad…(v)
E' P100 : storage elastic coefficient [ GPa ] of polyimide layer at 100 DEG C]
E' P200 : storage of polyimide layers at 200 DEG CCoefficient of elasticity [ GPa ]]
E' AD100 : storage elastic coefficient [ GPa ] of adhesive layer at 100deg.C]
E' AD200 : storage elastic coefficient [ GPa ] of adhesive layer at 200 DEG C]
t p1 : total thickness [ μm ] of thermoplastic polyimide layer and non-thermoplastic polyimide layer laminated on one side of adhesive layer ]
t p2 : total thickness [ μm ] of thermoplastic polyimide layer and non-thermoplastic polyimide layer laminated on the other side of the adhesive layer]
tad: thickness of adhesive layer [ mu ] m
Here, the coefficient of elasticity parameter P of the polyimide layer P To make the elastic coefficient parameter P P1 And coefficient of elasticity parameter P P2 The value obtained by addition, the coefficient of elasticity parameter P P1 The elastic modulus parameter P is calculated by the formula (iii) by taking the thermoplastic polyimide layer and the non-thermoplastic polyimide layer laminated on one side of the adhesive layer as one polyimide layer P2 The thermoplastic polyimide layer and the non-thermoplastic polyimide layer laminated on the other side of the adhesive layer are calculated by the formula (iv) with the one polyimide layer being regarded as one polyimide layer. }
c) The dielectric loss tangent at 20GHz, as measured by using a separation column dielectric resonator (split post dielectric resonators, SPDR), is less than 0.0029 as a whole.
In the multilayer film of the present invention, the polyimide layer obtained by laminating a thermoplastic polyimide layer laminated on one side of the adhesive layer and a non-thermoplastic polyimide may have a storage elastic modulus at 100℃of 1.0GPa or more and a storage elastic modulus at 200℃of 0.1GPa or more.
In the multilayer film of the present invention, the adhesive layer may have a storage elastic modulus at 100℃of less than 130MPa and a storage elastic modulus at 200℃of 40MPa or less.
In the multilayer film of the present invention, the total thickness of the thermoplastic polyimide layers in the entire multilayer film is T A The total thickness of the non-thermoplastic polyimide layers is set as T B Will stick toWhen the thickness of the junction layer is tad, the following formula (vi) can be satisfied.
0.60≦tad/(T A +T B +tad)≦0.99…(vi)
In the multilayer film of the present invention, the polyimide layer obtained by laminating the thermoplastic polyimide layer laminated on one side of the adhesive layer and the non-thermoplastic polyimide layer may have a thermal expansion coefficient in the range of 5ppm/K to 35 ppm/K.
In the multilayer film of the present invention, the adhesive layer may contain a thermoplastic polyimide and a polystyrene elastomer resin, and the content of the polystyrene elastomer resin may be in the range of 10 parts by weight to 150 parts by weight with respect to 100 parts by weight of the thermoplastic polyimide.
In the multilayer film of the present invention, the thermoplastic polyimide contained in the adhesive layer may contain an acid dianhydride residue derived from an acid dianhydride component and a diamine residue derived from a diamine component. In this case, the content of diamine residues derived from a dimer diamine composition containing a dimer diamine in which two terminal carboxylic acid groups of dimer acid are substituted with primary aminomethyl groups or amino groups as a main component may be 20 mol% or more based on the total diamine residues, and the content of diamine residues derived from a diamine compound represented by the following general formula (1) may be in the range of 5 mol% to 50 mol%.
[ chemical 1]
In formula (1), R independently represents a halogen atom, or an alkyl or alkoxy group which may be substituted with a halogen atom of 1 to 6 carbon atoms, or a phenyl or phenoxy group which may be substituted with a monovalent hydrocarbon group of 1 to 6 carbon atoms, Z independently represents a group selected from-O-, -S-, and CH 2 -、-CH(CH 3 )-、-C(CH 3 ) 2 -、-CO-、-COO-、-SO 2 Divalent radical-NH-or-NHCO-, m 1 Independently represents an integer of 0 to 4, m 2 And represents an integer of 0 to 2.
In the multilayer film of the present invention, the thermoplastic polyimide contained in the adhesive layer may be a crosslinked polyimide in which a ketone group contained in a molecular chain and an amino group of an amino compound having at least two primary amino groups as functional groups form a crosslinked structure through a c=n bond.
In the multilayer film of the present invention, the thermoplastic polyimide constituting the thermoplastic polyimide layer may contain an acid dianhydride residue derived from an acid dianhydride component and a diamine residue derived from a diamine component. In this case, the proportion of BPDA residues derived from 3,3', 4' -biphenyltetracarboxylic dianhydride (3, 3', 4' -biphenyl tetracarboxylic dianhydride, BPDA) may be 40 mol% or more with respect to the total acid dianhydride residues, and the proportion of diamine residues derived from the diamine compound represented by the general formula (1) may be 30 mol% or more with respect to the total diamine residues.
In the multilayer film of the present invention, the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer may contain an acid dianhydride residue derived from an acid dianhydride component and a diamine residue derived from a diamine component. In this case, the proportion of the acid dianhydride residues having a biphenyl skeleton may be 40 mol% or more with respect to the entire acid dianhydride residues, and the proportion of the diamine residues having a biphenyl skeleton may be 40 mol% or more with respect to the entire diamine residues.
The metal-clad laminate of the present invention comprises any one of the above-described multilayer films and a metal layer laminated on one or both surfaces of the multilayer film.
In the metal-clad laminate of the present invention, when the metal layer is etched and removed, the dimensional change rate of the multilayer film after etching may be within ±0.10% based on the multilayer film before etching, or within ±0.10% after heating at 150 ℃ for 30 minutes based on the multilayer film after etching.
The circuit board of the present invention is formed by processing the metal layer of any one of the metal-clad laminate boards into wiring.
A circuit board comprising an insulating resin layer and a wiring layer provided on at least one surface of the insulating resin layer, wherein the insulating resin layer is the multilayer film of any one of the above.
[ Effect of the invention ]
The multilayer film of the present invention can thin the whole outer layer portion by satisfying the conditions of a) to c), ensure dimensional stability, and improve the dielectric characteristics of the whole multilayer film. In particular, by the ratio (P under condition b P /P AD ) Satisfies the equation (i), and the elastic coefficient parameter (P) of the outer layer portion P ) Coefficient of elasticity parameter (P) of the inner layer portion AD ) The dimensional stability of the whole multilayer film is improved by controlling the multilayer film to be larger than a predetermined range. The effect of the present invention can be particularly effectively exhibited in a layer structure in which the total thickness or the thickness ratio of the polyimide layers as the outer layer portion is relatively small and the thickness or the thickness ratio of the adhesive layer is relatively large. In addition, as the resin constituting the inner layer portion, a resin excellent in dielectric characteristics and small in storage modulus at high temperature is used, whereby the relative thickness ratio of the inner layer portion can be increased while maintaining dimensional stability, and low dielectric loss tangent of the whole multilayer film can be achieved. Therefore, when the metal-clad laminate using the multilayer film of the present invention is applied to a circuit board for transmitting a high-frequency signal in the GHz band, it is possible to reduce transmission loss and improve reliability due to excellent dimensional stability.
Drawings
Fig. 1 is a schematic cross-sectional view showing the layer structure of a multilayer film according to a preferred embodiment of the present invention.
Fig. 2 is a schematic cross-sectional view showing a layer structure of a multilayer film according to another preferred embodiment of the present invention.
Fig. 3 is a schematic cross-sectional view showing the layer structure of a metal-clad laminate according to a preferred embodiment of the present invention.
Fig. 4 is a schematic cross-sectional view showing a layer structure of a metal clad laminate according to another preferred embodiment of the present invention.
[ description of symbols ]
10A, 10B, 30A, 30B: thermoplastic polyimide layer
20A, 20B: non-thermoplastic polyimide layer
40A: first insulating resin layer
40B: second insulating resin layer
100. 101: multilayer film
110A, 110B: metal layer
200. 201: metal-clad laminate
BS: adhesive layer
Detailed Description
Embodiments of the present invention will be described with appropriate reference to the accompanying drawings.
[ multilayer film ]
The multilayer film of the present invention comprises a plurality of polyimide layers and an adhesive layer, and has the following layer structure of (1) or (2):
(1) Thermoplastic polyimide layer/non-thermoplastic polyimide layer/adhesive layer/non-thermoplastic polyimide layer/thermoplastic polyimide layer,
or,
(2) Thermoplastic polyimide layer/non-thermoplastic polyimide layer/adhesive layer/thermoplastic polyimide layer/non-thermoplastic polyimide layer/thermoplastic polyimide layer.
Fig. 1 shows a cross-sectional structure of a multilayer film 100 according to an embodiment of the present invention. The multilayer film 100 has a layer structure in which a thermoplastic polyimide layer 10A/a non-thermoplastic polyimide layer 20A/an adhesive layer BS/a non-thermoplastic polyimide layer 20B/a thermoplastic polyimide layer 10B are sequentially laminated. Here, the thermoplastic polyimide layer 10A and the non-thermoplastic polyimide layer 20A of the outer layer portion on one side constitute a first insulating resin layer 40A, and the thermoplastic polyimide layer 10B and the non-thermoplastic polyimide layer 20B of the outer layer portion on the other side constitute a second insulating resin layer 40B. Therefore, the multilayer film 100 has a structure in which the first insulating resin layer 40A as an outer layer, the adhesive layer BS as an inner layer, and the second insulating resin layer 40B as an outer layer are laminated in this order.
Unlike the layer structure of the related art, the multilayer film 100 has a layer structure in which only one thermoplastic polyimide layer is laminated on each of the first insulating resin layer 40A and the second insulating resin layer 40B as the outer layer portions. In this way, by forming the outer layer portion on one side of the adhesive layer BS into a two-layer structure and integrating the thermoplastic polyimide layers (the thermoplastic polyimide layer 10A or the thermoplastic polyimide layer 10B) one by one on one side, the thickness of the outer layer portion can be reduced, and the adhesion between the metal layer and the metal layer can be ensured when the metal layer is laminated on the outside.
Fig. 2 shows a cross-sectional structure of a multilayer film 101 according to another preferred embodiment of the present invention. The multilayer film 101 has a layer structure in which a thermoplastic polyimide layer 10A/a non-thermoplastic polyimide layer 20A/a thermoplastic polyimide layer 30A/an adhesive layer BS/a thermoplastic polyimide layer 30B/a non-thermoplastic polyimide layer 20B/a thermoplastic polyimide layer 10B are laminated in this order.
Here, the thermoplastic polyimide layer 10A, the non-thermoplastic polyimide layer 20A, and the thermoplastic polyimide layer 30A constitute a first insulating resin layer 40A, and the thermoplastic polyimide layer 10B, the non-thermoplastic polyimide layer 20B, and the thermoplastic polyimide layer 30B constitute a second insulating resin layer 40B. Therefore, the multilayer film 101 has a structure in which the first insulating resin layer 40A, the adhesive layer BS, and the second insulating resin layer 40B are laminated in this order.
In the structural examples shown in fig. 1 and 2, the thermoplastic polyimide layer 10A, the thermoplastic polyimide layer 10B, the thermoplastic polyimide layer 30A, and the thermoplastic polyimide layer 30B may be made of the same or different types of thermoplastic polyimide. The non-thermoplastic polyimide layer 20A and the non-thermoplastic polyimide layer 20B may be made of the same or different kinds of non-thermoplastic polyimide. Details of the preferred polyimide used for the first insulating resin layer 40A and the second insulating resin layer 40B will be described later.
In addition, a hardening resin component such as a plasticizer or an epoxy resin, a hardening agent, a hardening accelerator, an organic or inorganic filler, a coupling agent, a flame retardant, or the like may be appropriately blended in the first insulating resin layer 40A and the second insulating resin layer 40B.
The multilayer film 100 and the multilayer film 101 satisfy the following conditions a) to c).
a) The total thickness of the thermoplastic polyimide layer and the non-thermoplastic polyimide layer laminated on one side of the adhesive layer is in the range of 2 μm to 20 μm.
In the structural example shown in fig. 1, the total thickness of the thermoplastic polyimide layer 10A and the non-thermoplastic polyimide layer 20A laminated on the side of the adhesive layer BS and the total thickness of the thermoplastic polyimide layer 10B and the non-thermoplastic polyimide layer 20B are each in the range of 2 μm to 20 μm. In the structural example shown in fig. 2, the condition a specifies that the total thickness of the thermoplastic polyimide layer 10A, the non-thermoplastic polyimide layer 20A, and the thermoplastic polyimide layer 30A, and the total thickness of the thermoplastic polyimide layer 10B, the non-thermoplastic polyimide layer 20B, and the thermoplastic polyimide layer 30B, which are laminated on one side of the adhesive layer BS, are all in the range of 2 μm to 20 μm. That is, in fig. 1 and 2, the thickness of the first insulating resin layer 40A and the thickness of the second insulating resin layer 40B are both in the range of 2 μm to 20 μm.
By setting the first insulating resin layer 40A and the second insulating resin layer 40B as the outer layer portions in a predetermined thickness range in this manner, the thickness/thickness ratio of the adhesive layer BS having relatively excellent dielectric characteristics can be increased as much as possible, and the dielectric characteristics of the multilayer film 100 and the multilayer film 101 as a whole can be improved. If the thickness of the first insulating resin layer 40A or the second insulating resin layer 40B is smaller than 2 μm, the adhesion between the metal layers is impaired when the metal layers are laminated on the outside, and if the thickness exceeds 20 μm, the thickness/thickness ratio of the adhesive layer BS is increased, which makes it difficult to reduce the dielectric loss tangent of the entire multilayer film 100 or 101. From the above viewpoints, the thickness of the first insulating resin layer 40A and the thickness of the second insulating resin layer 40B are each preferably in the range of 2 μm or more and 12 μm or less, more preferably in the range of 2 μm or more and 8 μm or less, and most preferably in the range of 2 μm or more and 5 μm or less.
In fig. 1 and 2, the thickness of the thermoplastic polyimide layer 10A and the thermoplastic polyimide layer 10B is preferably in the range of, for example, 0.5 μm or more and 3 μm or less, more preferably in the range of 1 μm or more and 2 μm or less, and still more preferably in the range of 1 μm or more and 1.8 μm or less, from the viewpoint of ensuring sufficient adhesion with the metal layer when the metal layer is laminated on the outside. In addition, from the viewpoint of securing self-supporting properties of the entire multilayer film 100 and the multilayer film 101 and suppressing excessive decrease in Coefficient of Thermal Expansion (CTE), the thickness of the non-thermoplastic polyimide layer 20A and the non-thermoplastic polyimide layer 20B is, for example, preferably in the range of 1 μm or more and 10 μm or less, more preferably in the range of 1 μm or more and 4 μm or less, still more preferably in the range of 1.5 μm or more and 5 μm or less, and most preferably in the range of 1.5 μm or more and 3 μm or less.
In fig. 2, the thickness of the thermoplastic polyimide layer 30A and the thermoplastic polyimide layer 30B is, for example, preferably in the range of 0.5 μm or more and 3 μm or less, more preferably in the range of 1 μm or more and 2 μm or less, from the viewpoints of adhesion to the adhesive layer BS and dielectric characteristics.
The thermoplastic polyimide layers 10A, 10B, 30A, 30B may have the same thickness or different thicknesses, and the non-thermoplastic polyimide layers 20A, 20B may have the same thickness or different thicknesses. Further, the first insulating resin layer 40A and the second insulating resin layer 40B may have the same thickness or may have different thicknesses.
b) The following formula (i) is satisfied.
65＜P P /P AD ＜1,550…(i)
{ here, P P Is the elasticity coefficient parameter of the polyimide layer, P AD The elastic modulus parameter of the adhesive layer is represented by the following formulas (ii) to (v):
P P ＝P P1 +P P2 …(ii)
P P1 ＝(E' P100 +E' P200 )×t p1 …(iii)
P P2 ＝(E' P100 +E' P200 )×t p2 …(iv)
P AD ＝(E' AD100 +E' AD200 )×tad…(v)
E' P100 : storage elastic coefficient [ GPa ] of polyimide layer at 100 DEG C]
E' P200 : storage elastic coefficient [ GPa ] of polyimide layer at 200 DEG C]
E' AD100 : storage elastic coefficient [ GPa ] of adhesive layer at 100deg.C]
E' AD200 : storage elastic coefficient [ GPa ] of adhesive layer at 200 DEG C]
t p1 : total thickness [ μm ] of thermoplastic polyimide layer and non-thermoplastic polyimide layer laminated on one side of adhesive layer ]
t p2 : total thickness [ μm ] of thermoplastic polyimide layer and non-thermoplastic polyimide layer laminated on the other side of the adhesive layer]
tad: thickness of adhesive layer [ mu ] m
Here, the coefficient of elasticity parameter P of the polyimide layer P To make the elastic coefficient parameter P P1 And coefficient of elasticity parameter P P2 The value obtained by addition, the coefficient of elasticity parameter P P1 The elastic modulus parameter P is calculated by the formula (iii) by taking the thermoplastic polyimide layer and the non-thermoplastic polyimide layer laminated on one side of the adhesive layer as one polyimide layer P2 The thermoplastic polyimide layer and the non-thermoplastic polyimide layer laminated on the other side of the adhesive layer are calculated by the formula (iv) with the one polyimide layer being regarded as one polyimide layer. }
Condition b specifies the coefficient of elasticity parameter (P) of the polyimide layer as the whole of the outer layer portion P ) An elastic modulus parameter (P relative to the adhesive layer BS as the inner layer portion AD ) Ratio (P) P /P AD ) Within a specified range. Coefficient of elasticity parameter (P) P ) For example, the total of the storage elastic coefficients and the thickness (P) of the first insulating resin layer 40A at 100 ℃ and 200 ℃ in the process temperature zone at the time of thermocompression bonding P1 ) And the sum of the storage elastic coefficients and the product (P) of the thickness of the second insulating resin layer 40B at the temperature P2 ) The value obtained by the addition. In addition, coefficient of elasticity parameter (P AD ) For example, the product of the sum of storage elastic coefficients and the thickness of the adhesive layer BS at 100 ℃ and 200 ℃ in the process temperature zone at the time of thermocompression bonding.
Here, the outer layer portion and the inner layer portion are formedRatio of coefficient of elasticity parameters (P P /P AD ) The meaning of the index will be described. Consider that: residual stress of each layer after thermocompression bonding, which changes in size before and after etching due to heat treatment at thermocompression bonding and etching treatment of the metal layer, is affected by differences in storage modulus of elasticity or thickness of each layer. That is, it is important that the storage elastic modulus of each layer is a storage elastic modulus of a process temperature band, and the storage elastic modulus greatly varies depending on the temperature, so that the higher the storage elastic modulus is, the greater the stress at the time of thermal expansion or thermal contraction becomes. In addition, regarding the thickness, it is considered that a layer having a large thickness ratio easily affects dimensional change. Since the adhesive layer BS in the inner layer portion has excellent dielectric characteristics as compared with the polyimide layer, the thickness ratio of the adhesive layer BS is increased to improve the dielectric characteristics of the multilayer film 100 and the multilayer film 101 as a whole, but in order to achieve both dimensional stability and dielectric characteristics at a high level, a method of controlling the optimum balance between the storage elastic modulus and the thickness of each layer has been studied for the outer layer portion and the inner layer portion, respectively, and as a result, it has been found that: parameters including the product of the sum of storage elastic coefficients at 100 ℃ and 200 ℃ as representative values of the storage elastic coefficients in the process temperature zone and the thickness of each layer are calculated, and the ratio of the parameters is controlled to a prescribed range, thereby exhibiting desired dimensional stability. Based on this finding, the coefficient of elasticity parameter (P P ) Coefficient of elasticity parameter (P) with respect to the adhesive layer BS AD ) Ratio (P) P /P AD ) The ratio of the residual stress of the outer layer portion to the residual stress of the inner layer portion is expressed by simplifying the storage elastic modulus, and the ratio (P P /P AD ) Satisfies the equation (i), and the elastic coefficient parameter (P) of the outer layer portion P ) Coefficient of elasticity parameter (P) of the inner layer portion AD ) The dimensional stability of the multilayer film 100 and the multilayer film 101 as a whole is improved by controlling the thickness to be larger than a predetermined range.
On the premise that the thickness of the outer layer portion satisfies the condition a, in the formula (i), if the ratio (P P /P AD ) If the temperature is 65 or less, thermocompression bondingIf the residual stress is 1,550 or more, the dimensional stability is maintained, but the dielectric loss tangent cannot be reduced, and the following condition c is difficult to be satisfied. In this respect, the ratio (P P /P AD ) The lower limit of (2) is preferably 70 or more, more preferably 80 or more, and most preferably 90 or more. In addition, the ratio (P P /P AD ) The upper limit of (2) is preferably 1200 or less, more preferably 900 or less, and most preferably 500 or less.
c) The dielectric loss tangent at 20GHz, as measured by SPDR resonator, is less than 0.0029 as the whole of the multilayer film.
Condition c specifies that the dielectric loss tangent of the multilayer film 100 and the multilayer film 101 as a whole is a very low value compared with the prior art. If the dielectric loss tangent at 20GHz of the entire multilayer film 100 or 101 is less than 0.0029, the loss of an electric signal can be effectively reduced on the transmission path of a high-frequency signal in the GHz band of 1GHz to 60GHz, for example, and thus the multilayer film can be applied to a circuit board used for high-speed communication after 5G communication, for example. From the above viewpoints, the dielectric loss tangent at 20GHz of the entire multilayer film 100 and 101 is preferably 0.0025 or less, and more preferably 0.0020 or less.
In the same manner, the relative dielectric constant of the entire multilayer film 100 and the multilayer film 101 at 20GHz measured using the SPDR resonator is preferably 3.0 or less, and more preferably in the range of 2.9 to 1.5.
The multilayer film 100 and the multilayer film 101 preferably satisfy one or more of the conditions d) to g) in addition to the conditions a) to c).
d) The polyimide layer formed by combining the thermoplastic polyimide layer and the non-thermoplastic polyimide layer laminated on one side of the adhesive layer has a storage elastic modulus of 1.0GPa or more at 100 ℃ and a storage elastic modulus of 0.1GPa or more at 200 ℃.
Condition d specifies: the storage elastic modulus at 100 ℃ is 1.0GPa or more and the storage elastic modulus at 200 ℃ is 0.1GPa or more for each of the first insulating resin layer 40A and the second insulating resin layer 40B. The satisfaction of the condition d means that the storage modulus of elasticity of the outer layer portion is higher than that of the adhesive layer BS as the inner layer portion in the thermocompression bonding temperature region (100 to 200 ℃). In order to suppress dimensional changes due to residual stress after thermocompression bonding, it is considered to be effective to increase the elastic modulus parameter of the outer layer portion by a certain amount or more with respect to the inner layer portion, and therefore, by considering the condition e described below, it is possible to improve the dimensional stability of the multilayer film 100 and the multilayer film 101 as a whole by controlling the storage elastic modulus of the outer layer portion to be larger than the storage elastic modulus of the inner layer portion. From the above viewpoints, the storage elastic coefficients at 100 ℃ of the first insulating resin layer 40A and the second insulating resin layer 40B are each preferably in the range of 2GPa to 10GPa, more preferably in the range of 3GPa to 8 GPa. The storage modulus of elasticity at 200℃is preferably in the range of 0.5GPa to 8GPa, more preferably in the range of 1GPa to 5 GPa.
The storage elastic coefficients of the first insulating resin layer 40A and the second insulating resin layer 40B may be the same or different, but are preferably the same from the viewpoint of suppressing warpage.
e) The adhesive layer has a storage elastic modulus at 100 ℃ of less than 130MPa and a storage elastic modulus at 200 ℃ of 40MPa or less.
Condition e defines the storage modulus of elasticity of the thermoplastic polyimide (hereinafter, sometimes referred to as "adhesive polyimide") constituting the adhesive layer BS in the thermocompression bonding temperature region (100 to 200 ℃). Meeting condition e means that the storage modulus of elasticity below 130MPa does not become excessively large in the temperature range of 100 ℃ to 200 ℃. It is considered that, after the metal layer is laminated on the outside, the residual stress after thermocompression bonding, which is the cause of dimensional change due to etching or heating of the metal layer, increases as the storage modulus of elasticity of the adhesive layer BS at the thermocompression bonding temperature increases, and increases as the thickness/thickness ratio of the adhesive layer BS increases. Therefore, by using a resin whose storage elastic modulus does not become excessively large in the thermocompression bonding temperature region, the residual stress after thermocompression bonding can be reduced and dimensional stability can be ensured even if the thickness/thickness ratio of the adhesive layer BS is increased to some extent. From the above viewpoint, the storage modulus of elasticity of the adhesive layer BS at 100 ℃ is preferably in the range of 0.01MPa to 100MPa, more preferably in the range of 0.1MPa to 50 MPa. The storage modulus of elasticity at 200℃is preferably in the range of 0.01MPa to 30MPa, more preferably in the range of 0.1MPa to 20 MPa.
f) When the total thickness of the thermoplastic polyimide layers in the whole multilayer film is T A The total thickness of the non-thermoplastic polyimide layers is set as T B When the thickness of the adhesive layer is tad, the following formula (vi) is satisfied,
0.60≦tad/(T A +T B +tad)≦0.99…(vi)
condition f specifies that the thickness tad of the adhesive layer BS is set to be equal to the thickness (T A +T B The ratio tad/(T) of + tad A +T B + tad) is set within a predetermined range. Here, the thickness T A The total thickness of the thermoplastic polyimide layers 10A and 10B in fig. 1 or the total thickness of the thermoplastic polyimide layers 10A, 10B, 30A and 30B in fig. 2 is the thickness T in fig. 1 and 2 B The combined thickness of the non-thermoplastic polyimide layer 20A and the non-thermoplastic polyimide layer 20B.
By making the thickness ratio tad/(T) A +T B + tad) satisfies the formula (vi), and the multilayer film 100 and the multilayer film 101 as a whole can be reduced in dielectric loss tangent and balanced with dimensional stability. If the thickness ratio tad/(T) A +T B If + tad) is less than 0.60, the thickness ratio of the adhesive layer BS becomes relatively small, and therefore the low dielectric loss tangent of the entire multilayer film 100 and the multilayer film 101 becomes difficult, and the transmission loss at the time of high-frequency signal transmission becomes large. From the point of view, the thickness ratio tad/(T) A +T B The lower limit value of + tad) is preferably 0.65 or more, more preferably 0.70 or more, still more preferably 0.80 or more, and most preferably 0.85 or more.
On the other hand, at the thickness ratio tad/(T) A +T B + tad) is higher than 0.99, the thickness ratio of the adhesive layer BSThe relative increase in size makes it difficult to ensure adhesion to the metal layer and also makes it difficult to maintain the dimensional stability of the entire multilayer film 100 and 101. Thus, the thickness ratio tad/(T) A +T B The upper limit value of + tad) is preferably 0.96 or less, more preferably 0.94 or less.
The thickness (T A +T B + tad) is, for example, preferably in the range of 70 μm to 500 μm, more preferably in the range of 100 μm to 300 μm. If the thickness (T A +T B If + tad) is less than 70 μm, the effect of suppressing the transmission loss of the high-frequency signal is insufficient when the circuit board is manufactured, and if it exceeds 500 μm, the productivity may be lowered.
In addition, the thickness tad of the adhesive layer BS is preferably greater than 50 μm. The effect of the present invention, which combines excellent dielectric characteristics and dimensional stability, is particularly effectively exhibited in a laminated structure in which the thickness tad of the adhesive layer BS is greater than 50 μm. From the above point of view, the thickness tad of the adhesive layer BS is, for example, preferably in the range of 50 μm to 450 μm, more preferably in the range of 60 μm to 250 μm. If the thickness tad of the adhesive layer BS is less than the lower limit, the low dielectric loss tangent may be insufficient, and thus, sufficient dielectric characteristics may not be obtained. On the other hand, if the thickness tad of the adhesive layer BS exceeds the upper limit, there may be a problem such as a decrease in dimensional stability.
g) When the total thickness of the thermoplastic polyimide layers in the whole multilayer film is T A The total thickness of the non-thermoplastic polyimide layers is set as T B When the following formula (vii) is satisfied.
0.1≦(T A )/(T A +T B )≦0.6…(vii)
Condition g specifies the total thickness T A Relative to the sum (T) A +T B ) The ratio of (2) is set to be within a predetermined range. Here, (T) A +T B ) The total thickness of the outer layer portions provided on both sides of the adhesive layer BS (i.e., the total thickness of the first insulating resin layer 40A and the second insulating resin layer 40B). Thus, the thermoplastic polyimide in the whole outer layer partTotal thickness ratio of amine layers (T A )/(T A +T B ) The expression (vii) is satisfied, and even if the thicknesses of the first insulating resin layer 40A and the second insulating resin layer 40B as the outer layer portions are reduced in thickness as compared with the conventional art under the condition a, the outer layer portions can be suppressed from excessively lowering CTE, and the adhesion to the metal layer can be sufficiently ensured when the metal layer is laminated on the outside.
The non-thermoplastic polyimide layers 20A and 20B contained in the outer layer portion tend to have a smaller thickness and a lower Coefficient of Thermal Expansion (CTE). This tendency is remarkably seen in the case where the non-thermoplastic polyimide layer 20A and the non-thermoplastic polyimide layer 20B are formed by a casting method. This is thought to be because the thinner the coating film thickness during the heat treatment, the more the solvent evaporates and the molecules are oriented. Therefore, if the thickness ratio (T A )/(T A +T B ) If the CTE is less than 0.1, the CTE of the outer layer portion is excessively lowered, and when the metal layer is laminated on the outside, it may be difficult to secure adhesion with the metal layer. From the point of view, the thickness ratio (T A )/(T A +T B ) The lower limit value of (2) is preferably selected from, for example, any one of 0.17, 0.20, 0.25, 0.30 or 0.40.
On the other hand, in the thickness ratio (T A )/(T A +T B ) If the amount exceeds 0.6, for example, when the metal layer is etched after the metal layer is laminated on the outside, or when the metal layer is subjected to heat treatment, it may be difficult to maintain the dimensional stability of the entire multilayer film 100 or 101. Thus, the thickness ratio (T A )/(T A +T B ) The upper limit of (2) is preferably 0.55 or less, more preferably 0.50 or less.
When the multilayer film 100 or the multilayer film 101 is used as an insulating resin layer of a circuit board, for example, the Coefficient of Thermal Expansion (CTE) of the entire film is preferably in the range of 10ppm/K to 30ppm/K, more preferably in the range of 10ppm/K to 25ppm/K, and most preferably in the range of 10ppm/K to 20ppm/K, in order to prevent occurrence of warpage or decrease in dimensional stability. If the CTE is less than 10ppm/K or exceeds 30ppm/K, warpage or a decrease in dimensional stability occurs.
In addition, for example, in the case of application as an insulating resin layer of a circuit board, in order to prevent occurrence of warpage or reduction in dimensional stability, the Coefficient of Thermal Expansion (CTE) of the first insulating resin layer 40A or the second insulating resin layer 40B laminated on one side of the adhesive layer BS is preferably in the range of 5ppm/K to 35ppm/K, more preferably in the range of 8ppm/K to 30ppm/K, and most preferably in the range of 10ppm/K to 25ppm/K, respectively.
The Coefficient of Thermal Expansion (CTE) of the first insulating resin layer 40A and that of the second insulating resin layer 40B may be the same or different, but are preferably the same from the viewpoint of suppressing warpage.
[ polyimide ]
Next, polyimide constituting the first insulating resin layer 40A, the second insulating resin layer 40B, and the adhesive layer BS will be described.
In the present invention, the term "polyimide" refers to a resin containing a polymer having an imide group in its molecular structure, such as polyamide imide, polyether imide, polyester imide, polysiloxane imide, and polybenzimidazole imide, in addition to polyimide. In the case where the polyimide has a plurality of structural units, the polyimide may exist as a block or may exist randomly, but is preferably randomly.
In addition, "thermoplastic polyimide" generally means a polyimide whose glass transition temperature (Tg) can be clearly confirmed, and in the present invention, it means that the storage modulus of elasticity at 30℃is 1.0X10 when measured using a dynamic viscoelasticity measuring apparatus (dynamic thermo-mechanical analyzer (Dynamic thermomechanical analyzer, DMA)) 9 A storage elastic modulus at 300 ℃ of less than 1.0X10 and Pa or above 8 Polyimide of Pa. The term "non-thermoplastic polyimide" refers to a polyimide which does not normally exhibit softening and adhesion even when heated, but in the present invention, it refers to a polyimide having a storage modulus of elasticity of 1.0X10 at 30℃as measured by a dynamic viscoelasticity measuring Device (DMA) 9 A storage elastic modulus at 300 ℃ of 1.0X10 at Pa or above 8 Polyimide of Pa or more.
< thermoplastic polyimide >)
The thermoplastic polyimide used to form the thermoplastic polyimide layers 10A, 10B, 30A, 30B of the first and second insulating resin layers 40A, 40B is obtained by reacting an acid dianhydride component with a diamine component including an aliphatic diamine and/or an aromatic diamine, and contains an acid dianhydride residue derived from the acid dianhydride component and a diamine residue derived from the diamine component. The thermal expansibility, adhesiveness, glass transition temperature, and the like of the thermoplastic polyimide can be controlled by selecting the types of the acid dianhydride component and the diamine component and the molar ratio of the two or more kinds of the acid anhydride or diamine to be used. In addition, in the present invention, "acid dianhydride residue" refers to a tetravalent group derived from acid dianhydride, and "diamine residue" refers to a divalent group derived from a diamine compound.
In the thermoplastic polyimide used for forming the thermoplastic polyimide layers 10A, 10B, 30A, and 30B, the acid dianhydride component and the diamine component which are monomers generally used for synthesizing the thermoplastic polyimide can be used as raw materials, but aromatic acid dianhydride or aromatic diamine is preferably used.
As the aromatic acid dianhydride, for example, pyromellitic dianhydride (Pyromellitic dianhydride, PMDA), 3', 4' -benzophenone tetracarboxylic dianhydride (3, 3', 4' -benzophenone tetracarboxylic dianhydride, BTDA), 3', 4' -biphenyl tetracarboxylic dianhydride (BPDA), 2,3',3,4' -biphenyltetracarboxylic dianhydride, p-phenylene bis (trimellitic monoester) anhydride (TAHQ), 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride (2, 2-bis [4- (3, 4-dicarboxyphenoxy ] propane dianhydride, BPADA) and the like.
The content of the 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA) residues derived from BPDA is preferably 40 mol% or more, more preferably 45 mol% to 80 mol% based on the total acid dianhydride residues, while improving the dielectric characteristics so as to reduce the concentration of the polar groups, and ensuring the adhesion to the substrate.
The aromatic diamine is preferably a diamine compound represented by the following general formula (1) from the viewpoint of ensuring proper flexibility and adhesion to a substrate.
[ chemical 1]
In the general formula (1), R independently represents a halogen atom, or an alkyl group or an alkoxy group which may be substituted with a halogen atom of 1 to 6 carbon atoms, or a phenyl group or a phenoxy group which may be substituted with a monovalent hydrocarbon group or an alkoxy group of 1 to 6 carbon atoms, Z independently represents a group selected from the group consisting of-O-, -S-, -CH 2 -、-CH(CH 3 )-、-C(CH 3 ) 2 -、-CO-、-COO-、-SO 2 Divalent radical-NH-or-NHCO-, m 1 Independently represents an integer of 0 to 4, m 2 And represents an integer of 0 to 2.
Examples of the diamine compound represented by the general formula (1) include: 1,3-bis (4-aminophenoxy) benzene (1, 3-bis (4-aminophenoxy) benzene, TPE-R), 1,4-bis (4-aminophenoxy) benzene (1, 4-bis (4-aminophenoxy) benzene, TPE-Q), 1,3-bis (3-aminophenoxy) benzene (1, 3-bis (3-aminophenoxy) benzene, APB), 2-bis [4- (4-aminophenoxy) phenyl ] propane (2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, BAPP), bis [4- (4-aminophenoxy) phenyl ] sulfone (bis [4- (4-aminophenoxy) phenyl ] sulfofone, BAPS), 1,3-bis [2- (4-aminophenyl) -2-propyl ] benzene (bis-aniline-M), 4' -diaminodiphenyl ether (DAP), and the like.
In the thermoplastic polyimide layer 10A, the thermoplastic polyimide layer 10B, the thermoplastic polyimide layer 30A, and the thermoplastic polyimide layer 30B, the content of the diamine residue derived from the diamine compound represented by the general formula (1) is preferably 30 mol% or more, more preferably 50 mol% or more, and even more preferably 70 mol% to 90 mol% with respect to the total diamine residue, in terms of ensuring adhesion to the metal layer when the metal layer is laminated even if the thickness is reduced.
< non-thermoplastic polyimide >)
The non-thermoplastic polyimide used for forming the non-thermoplastic polyimide layer 20A and the non-thermoplastic polyimide layer 20B in the first insulating resin layer 40A and the second insulating resin layer 40B is obtained by reacting an acid dianhydride component with a diamine component including an aliphatic diamine and/or an aromatic diamine, and contains an acid dianhydride residue derived from the acid dianhydride component and a diamine residue derived from the diamine component. The thermal expansibility, dielectric characteristics, and the like of the non-thermoplastic polyimide can be controlled by selecting the types of the acid dianhydride component and the diamine component and the molar ratio of the two or more kinds of acid anhydrides or diamines to be used.
In the non-thermoplastic polyimide used for forming the non-thermoplastic polyimide layer 20A and the non-thermoplastic polyimide layer 20B, an acid dianhydride component and a diamine component, which are monomers generally used for synthesizing the non-thermoplastic polyimide, may be used, but from the viewpoint of controlling the Coefficient of Thermal Expansion (CTE) of the outer layer portion and securing dimensional stability, it is preferable to use an aromatic acid dianhydride having a biphenyl skeleton or an aromatic diamine having a biphenyl skeleton. The aromatic acid dianhydride having a biphenyl skeleton is preferably, for example, 3', 4' -biphenyl tetracarboxylic dianhydride (BPDA), 2,3',3,4' -biphenyl tetracarboxylic dianhydride, or the like, and particularly preferably, 3', 4' -biphenyl tetracarboxylic dianhydride (BPDA).
In the non-thermoplastic polyimide layer 20A and the non-thermoplastic polyimide layer 20B, the content ratio of the acid dianhydride residue having a biphenyl skeleton is preferably 40 mol% or more, more preferably 45 mol% to 70 mol% with respect to the total acid dianhydride residue, in order to control the Coefficient of Thermal Expansion (CTE) of the outer layer portion to ensure the dimensional stability of the multilayer film 100 and the multilayer film 101 as a whole and to improve the storage elasticity coefficient of the outer layer portion so as to satisfy the condition d.
The aromatic diamine having a biphenyl skeleton is preferably, for example, 2' -dimethyl-4,4' -diaminobiphenyl (2, 2' -dimethyl-4,4' -diaminobiphenyl, m-TB), 2' -diethyl-4,4' -diaminobiphenyl (2, 2' -diethyl-4,4' -diaminobiphenyl, m-EB), 2' -diethoxy-4,4' -diaminobiphenyl (2, 2' -diethoxy-4,4' -diaminobiphenyl, m-EOB), 2' -dipropoxy-4,4' -diaminobiphenyl (2, 2' -dipropoxy-4,4' -diaminobiphenyl), m-POB), 2' -di-n-propyl-4, 4' -diaminobiphenyl (2, 2' -n-propyl-4,4' -diaminobiphenyl, m-NPB), 2' -divinyl-4,4' -diaminobiphenyl (2, 2' -divinyl-4,4' -diaminobiphenyl, VAB), 4' -diaminobiphenyl, 4' -diamino-2,2' -bis (trifluoromethyl) biphenyl (4, 4' -diamido-2, 2' -bis (trifluoromethyl) biphenyl, TFMB), and the like, with 2,2' -dimethyl-4,4' -diaminobiphenyl (m-TB) being particularly preferred.
In the non-thermoplastic polyimide layer 20A and the non-thermoplastic polyimide layer 20B, the content ratio of the diamine residue having a biphenyl skeleton is preferably 40 mol% or more, more preferably 70 mol% to 100 mol% with respect to the entire diamine residue, in order to control the Coefficient of Thermal Expansion (CTE) of the outer layer portion to ensure the dimensional stability of the multilayer film 100 and the multilayer film 101 as a whole and to improve the storage modulus of elasticity of the outer layer portion so as to satisfy the condition d.
< adhesive polyimide >)
The adhesive polyimide which is a preferable resin constituting the adhesive layer BS is a thermoplastic polyimide obtained by reacting an acid dianhydride component with a diamine component containing an aliphatic diamine.
As the acid dianhydride component which is a raw material of the adhesive polyimide, monomers which are generally used in the synthesis of thermoplastic polyimide can be used, and for example, 3',4,4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), 3', 4' -diphenyl sulfone tetracarboxylic dianhydride (3, 3', 4' -diphenylsulfone tetracarboxylic dianhydride, DSDA), 4'-oxydiphthalic anhydride (4, 4' -oxydiphthalic dianhydride, ODPA), 4'- (hexafluoroisopropylidene) diphthalic anhydride (4, 4' - (hexafluorooisopropylene) diphthalic anhydride,6 FDA), 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride (2, 2-bis [4- (3, 4-dicarboxyphenoxy ] propane dianhydride, BPADA), p-phenylene bis (trimellitic monoester) anhydride (TAHQ), ethylene glycol bis trimellitic anhydride (ethylene glycol bistrimellitic anhydride, TMEG), 3', 4' -biphenyltetracarboxylic dianhydride (BPDA), 2,3',3,4' -biphenyltetracarboxylic dianhydride and the like, more preferably 3,3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA). The adhesive polyimide preferably contains one or more acid dianhydride residues derived from the aromatic acid dianhydride in a total of 40 to 100 mol% with respect to the total acid dianhydride residues, more preferably 50 to 90 mol% with respect to the total acid dianhydride residues, still more preferably contains two acid dianhydride residues derived from the aromatic acid dianhydride in a total of 40 to 100 mol% with respect to the total acid dianhydride residues, most preferably, the 3,3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) is contained in the range of 50 to 90 mol%, and the aromatic acid dianhydride other than BTDA is contained in the range of 10 to 50 mol%.
As the diamine component that is a raw material of the adhesive polyimide, a monomer that is generally used for the synthesis of the thermoplastic polyimide can be used, but it is preferable to use a dimer diamine composition in terms of controlling the storage modulus of the adhesive layer BS to satisfy the conditions b and e, reducing the dielectric loss tangent, and improving the dielectric characteristics of the multilayer film 100 and the multilayer film 101 as a whole to satisfy the condition c.
That is, the adhesive polyimide preferably contains diamine residues derived from the dimer diamine composition in a range of preferably 20 mol% or more, more preferably 50 mol% or more, and most preferably 70 mol% to 100 mol% with respect to the total diamine residues. By containing the diamine residue derived from the dimer diamine composition in the above amount, improvement of thermocompression bonding characteristics due to lowering of the glass transition temperature (lowering of Tg) of the adhesive layer BS can be achieved, further relaxation of internal stress due to lowering of the elastic modulus can be achieved, and dielectric characteristics of the adhesive layer BS can be improved. If the content of the diamine residue derived from the dimer diamine composition is less than 20 mol% relative to the total diamine residues, the transmission loss at the time of high frequency transmission may be increased, or sufficient adhesiveness may not be obtained as the adhesive layer BS interposed between the first insulating resin layer 40A and the second insulating resin layer 40B.
The dimer diamine composition may contain the following component (a) as a main component, and may contain a mixture of the component (b) and the component (c), and is a purified product in which the amounts of the component (b) and the component (c) are controlled.
(a) Dimer diamine
(b) Monoamine compound obtained by substituting terminal carboxylic acid group of monoacid compound having 10-40 carbon atoms with primary aminomethyl group or amino group
(c) Amine compound obtained by substituting terminal carboxylic acid group of polybasic acid compound having hydrocarbon group in the range of carbon number 41 to 80 with primary aminomethyl group or amino group (wherein the dimer diamine is excluded)
(a) The dimer diamine of the component (C) refers to dimer acid wherein the two terminal carboxylic acid groups (-COOH) are primary aminomethyl groups (-CH) 2 -NH 2 ) Or amino (-NH) 2 ) Substituted diamines. Dimer acid is a known dibasic acid obtained by intermolecular polymerization of unsaturated fatty acids, and industrial production processes thereof have been generally standardized in the industry, and can be obtained by dimerization of unsaturated fatty acids having 11 to 22 carbon atoms with a clay catalyst or the like. The industrially available dimer acid mainly contains dibasic acids having 36 carbon atoms obtained by dimerization of unsaturated fatty acids having 18 carbon atoms such as oleic acid, linoleic acid, linolenic acid, etc., and, depending on the degree of purification, any amounts of monomeric acids (having 18 carbon atoms), trimeric acids (having 54 carbon atoms), and other polymerized fatty acids having 20 to 54 carbon atoms. In addition, although double bonds remain after the dimerization reaction, in the present invention, the dimer acid also contains a compound which further undergoes hydrogenation reaction to reduce the degree of unsaturation. (a) The dimer diamine of the component (a) may be defined as a diamine compound obtained by substituting the terminal carboxylic acid group of a dibasic acid compound having a carbon number in the range of 18 to 54, preferably 22 to 44, with a primary aminomethyl group or an amino group.
The dimer diamine may be characterized by imparting a characteristic of a skeleton derived from dimer acid. That is, since dimer diamine is an aliphatic group of a large molecule having a molecular weight of about 560 to 620, the molar volume of the molecule can be increased and the polar groups of polyimide can be relatively reduced. The characteristic of such dimer diamine is considered to contribute to suppression of a decrease in heat resistance of polyimide, and improvement in dielectric characteristics by reduction in relative permittivity and dielectric loss tangent. Further, since the polyimide contains two hydrophobic chains having 7 to 9 carbon atoms which are free to move and two chain aliphatic amino groups having a length close to 18 carbon atoms, it is considered that the polyimide can be provided with flexibility and can have an asymmetric chemical structure or a nonplanar chemical structure, and thus the dielectric constant of the polyimide can be reduced.
The dimer diamine composition is preferably a dimer diamine composition comprising: the dimer diamine content of the component (a) is increased to 96% by weight or more, preferably 97% by weight or more, more preferably 98% by weight or more by a purification method such as molecular distillation. By setting the dimer diamine content of the component (a) to 96% by weight or more, the molecular weight distribution of the polyimide can be suppressed from expanding. If technically feasible, the dimer diamine composition is preferably composed of the dimer diamine of component (a) in its entirety (100 wt%).
The sum of the component (b) and the component (c) of the dimer diamine composition may be 4% or less, preferably less than 4%, based on the area percentage of the chromatogram obtained by measurement by gel permeation chromatography (gel permeation chromatography, GPC). The percentage of the area of the chromatogram of the component (b) may be preferably 3% or less, more preferably 2% or less, further preferably 1% or less, and the percentage of the area of the chromatogram of the component (c) may be preferably 2% or less, more preferably 1.8% or less, further preferably 1.5% or less. By setting the range, a rapid increase in the molecular weight of polyimide can be suppressed, and further, an increase in the dielectric loss tangent of the resin film at a wide frequency can be suppressed. The component (b) and the component (c) may not be contained in the dimer diamine composition.
Examples of the dimer diamine composition include a commercially available product such as Pr Li Amin (PRIAMINE) 1073 (trade name) manufactured by Croda Japan (Croda Japan), pr Li Amin (PRIAMINE) 1074 (trade name) manufactured by Croda Japan (Croda Japan), and Pr Li Amin (PRIAMINE) 1075 (trade name) manufactured by Croda Japan (Croda Japan). In the case of using these commercial products, it is preferable to perform the purification for the purpose of reducing the content of components other than dimer diamine, and for example, it is preferable to set the content of dimer diamine to 96% by weight or more. The purification method is not particularly limited, and is preferably a known method such as distillation or precipitation purification.
The adhesive polyimide may be prepared by using a diamine compound other than the dimer diamine composition as a raw material within a range that does not impair the effect of the invention. The diamine compound represented by the general formula (1) is exemplified as a preferable diamine compound which can be used for the adhesive polyimide.
Among the diamine compounds represented by the general formula (1), the adhesive polyimide preferably contains, for example, 1, 3-bis (4-aminophenoxy) benzene (TPE-R), 1, 4-bis (4-aminophenoxy) benzene (TPE-Q), 1, 3-bis (3-aminophenoxy) benzene (APB), 2-bis [4- (4-aminophenoxy) phenyl ] propane (BAPP), bis [4- (4-aminophenoxy) phenyl ] sulfone (BAPS), and the like.
In the adhesive polyimide, in order to improve the flexibility of the adhesive layer BS, the residual stress after thermocompression bonding due to the low elastic modulus is relaxed, and the content of the diamine residue derived from the diamine compound represented by the general formula (1) is preferably in the range of 5 to 50 mol%, more preferably in the range of 10 to 30 mol%, with respect to the total diamine residue.
The thermal expansion coefficient, glass transition temperature, dielectric characteristics, and the like can be controlled by selecting the types of the acid dianhydride component and the diamine component in the adhesive polyimide, or the molar ratio of the two or more types of the acid dianhydride or diamine.
The weight average molecular weight of the adhesive polyimide is, for example, preferably in the range of 10,000 ～ 400,000, more preferably in the range of 20,000 ～ 350,000. If the weight average molecular weight is less than 10,000, the strength of the adhesive layer BS tends to be low and embrittlement tends to occur. On the other hand, if the weight average molecular weight exceeds 400,000, the viscosity excessively increases, and defects such as uneven thickness and streaks of the adhesive layer BS tend to occur during the coating operation.
The adhesive polyimide is most preferably a structure that is fully imidized. However, one of polyimidePart of the reaction mixture may be amic acid. The imidization ratio can be measured by using a Fourier transform infrared spectrophotometer (commercially available product: FT/IR620 manufactured by Japanese Spectroscopy) and measuring the infrared absorption spectrum of a polyimide film by a primary reflection ATR method at 1015cm -1 Based on the nearby benzene ring absorber, according to 1780cm -1 C=o from imide groups.
The glass transition temperature (Tg) of the adhesive polyimide is preferably 250 ℃ or lower, more preferably 40 ℃ or higher and 200 ℃ or lower. Since thermocompression bonding can be performed at a low temperature by setting the Tg of the adhesive polyimide to 250 ℃ or less, internal stress generated during lamination can be relaxed, and dimensional change after circuit processing can be suppressed. If Tg of the adhesive polyimide exceeds 250 ℃, the temperature at the time of adhesion between the first insulating resin layer 40A and the second insulating resin layer 40B becomes high, and there is a possibility that dimensional stability after circuit processing may be impaired.
By using the adhesive polyimide as described above, the adhesive layer BS has excellent flexibility and dielectric characteristics (low dielectric constant and low dielectric loss tangent).
In the adhesive layer BS, a polystyrene elastomer is preferably blended together with an adhesive polyimide. The polystyrene elastomer is a copolymer of styrene or a derivative thereof and a conjugated diene compound, including a hydride thereof. Here, styrene or its derivative is not particularly limited, and examples thereof may be given: styrene, methyl styrene, butyl styrene, divinylbenzene, vinyl toluene, and the like. The conjugated diene compound is not particularly limited, and examples thereof include: butadiene, isoprene, 1, 3-pentadiene, and the like.
In addition, the polystyrene elastomer is preferably hydrogenated. By hydrogenation, thermal stability is further improved, degradation such as decomposition and polymerization is less likely to occur, aliphatic properties are improved, and compatibility with adhesive polyimide is improved.
The copolymer structure of the polystyrene elastomer can be a block structure or a random structure. Preferable specific examples of the polystyrene elastomer include: styrene-butadiene-styrene block copolymers (SBS), styrene-butadiene-butylene-styrene block copolymers (SBBS), styrene-ethylene-butylene-styrene block copolymers (SEBS), styrene-ethylene-propylene-styrene block copolymers (SEPS), styrene-ethylene-ethylene/propylene-styrene block copolymers (SEEPS), and the like, but are not limited to these specific examples.
The weight average molecular weight of the polystyrene elastomer is, for example, preferably in the range of 50,000 ～ 300,000, more preferably in the range of 80,000 ～ 270,000. If the weight average molecular weight is less than the above range, the effect of improving the dielectric characteristics may be insufficient, whereas if the weight average molecular weight is more than the above range, the viscosity at the time of producing a composition comprising an adhesive polyimide and a solvent may be high, and the production of a resin film may be difficult.
In order to achieve a large degree of low dielectric loss tangent of the resin film, the polystyrene elastomer preferably has a weight average molecular weight of 100,000 or less, more preferably within a range of 50,000 ～ 100,000, and most preferably within a range of 70,000 ～ 100,000. By setting the weight average molecular weight of the polystyrene elastomer to 100,000 or less, the dielectric characteristics of the resin film can be greatly improved.
The acid value of the polystyrene elastomer is, for example, preferably 10mgKOH/g or less, more preferably 1mgKOH/g or less, and still more preferably 0mgKOH/g. By blending a polystyrene elastomer having an acid value of 10mgKOH/g or less, the dielectric loss tangent at the time of forming a resin film can be reduced, and good peel strength can be maintained. On the other hand, if the acid value exceeds 10mgKOH/g, the dielectric properties become poor and the compatibility with the adhesive polyimide becomes poor due to the increase of the polar groups, and the adhesion at the time of forming the resin film is lowered. Therefore, the lower the acid value, the better, and the substances which are not acid-modified (i.e., resins having an acid value of 0 mgKOH/g) are most suitable. In the present invention, since the adhesive polyimide can exhibit excellent adhesion when it contains a residue derived from an aliphatic diamine, a decrease in adhesive strength can be avoided even if a polystyrene elastomer which has not been acid-modified (i.e., has a strong aliphatic property) is used.
The polystyrene elastomer is preferably a styrene unit [ -CH ] 2 CH(C 6 H 5 )-]The content ratio of (2) is in the range of 10 wt% to 65 wt%, more preferably in the range of 20 wt% to 65 wt%, and most preferably in the range of 30 wt% to 60 wt%. If the content of the styrene unit in the polystyrene elastomer is less than 10% by weight, the elastic modulus of the resin is lowered, and if the content is greater than 65% by weight, the resin becomes rigid and difficult to use as an adhesive, and besides, the rubber component in the polystyrene elastomer is reduced, resulting in deterioration of the dielectric characteristics.
Further, since the content ratio of the styrene unit is within the above range, the proportion of the aromatic ring in the resin film becomes high, and therefore, when the through hole (through hole) and the blind hole are formed by laser processing in the process of manufacturing the circuit board using the resin film, the absorptivity in the ultraviolet region can be improved, and the laser processability can be further improved.
The polystyrene elastomer may be selected from commercially available ones. As such a commercially available polystyrene elastomer, for example, a1535HU (trade name), a1536HU (trade name), a 1652MU (trade name), a G1726VS (trade name), a G1645VS (trade name), an FG1901GT (trade name), a G1650MU (trade name), a G1654HU (trade name), a G1730VO (trade name), a MD1653MO (trade name) manufactured by KRATON (KRATON) company, and the like can be preferably used. Among these, as the polystyrene elastomer having a weight average molecular weight of 100,000 or less, MD1653MO (trade name), G1726VS (trade name), and the like manufactured by Koteng (KRATON) are more preferably used.
The content of the polystyrene elastomer is preferably in the range of 10 parts by weight or more and 150 parts by weight or less, more preferably in the range of 50 parts by weight or more and 120 parts by weight or less, relative to 100 parts by weight of the adhesive polyimide. When the content of the polystyrene elastomer is less than 10 parts by weight relative to 100 parts by weight of the adhesive polyimide, the effect of lowering the dielectric loss tangent may not be sufficiently exhibited. On the other hand, if the weight ratio of the polystyrene elastomer exceeds 150 parts by weight, the adhesiveness at the time of forming the resin film may be lowered, and the solid content concentration at the time of forming the composition containing the adhesive polyimide and the solvent may become excessively high, and the viscosity may be increased, and the handleability may be lowered.
The total content of the adhesive polyimide and the polystyrene elastomer is preferably 60 to 100% by weight, more preferably 80 to 100% by weight, of the total resin components constituting the adhesive layer BS.
In addition, in addition to the polystyrene elastomer, a curing resin component such as a plasticizer or an epoxy resin, a curing agent, a curing accelerator, an organic or inorganic filler, a coupling agent, a flame retardant, and the like may be appropriately blended in the adhesive layer BS.
< Synthesis of polyimide >
Thermoplastic polyimide, non-thermoplastic polyimide, and adhesive polyimide constituting the first insulating resin layer 40A and the second insulating resin layer 40B, and the adhesive polyimide constituting the adhesive layer BS can be manufactured as follows: the acid dianhydride and the diamine compound are reacted in a solvent, and after the polyamic acid is generated, the ring is closed by heating. For example, the acid dianhydride component and the diamine compound are dissolved in an organic solvent in approximately equimolar amounts, and the mixture is stirred at a temperature in the range of 0 to 100 ℃ for 30 minutes to 24 hours to perform polymerization, whereby polyamic acid as a precursor of polyimide can be obtained. In the reaction, the reaction components are dissolved so that the amount of the precursor to be formed is in the range of 5 to 50 wt%, preferably 10 to 40 wt%, in the organic solvent. Examples of the organic solvent used in the polymerization reaction include: n, N-dimethylformamide (N, N-dimethyl formamide, DMF), N-dimethylacetamide (N, N-dimethyl acetamide, DMAc), N-diethylacetamide, N-methyl-2-pyrrolidone (NMP), 2-butanone, dimethylsulfoxide (dimethyl sulfoxide, DMSO), hexamethylphosphoramide, N-methylcaprolactam, dimethyl sulfate, cyclohexanone, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), cresol and the like. These solvents may be used in combination of two or more kinds, and further, aromatic hydrocarbons such as xylene and toluene may be used in combination. The amount of the organic solvent used is not particularly limited, and is preferably adjusted so that the concentration of the polyamic acid solution obtained by the polymerization reaction is about 5 to 50% by weight.
The polyamic acid synthesized is advantageously used as a reaction solvent solution, and may be concentrated, diluted, or replaced with other organic solvents as needed. In addition, polyamide acid is generally excellent in solvent solubility, and thus is advantageously used. The viscosity of the solution of the polyamic acid is preferably in the range of 500 mPas to 100,000 mPas. When the thickness is outside the above range, defects such as uneven thickness and streaks are likely to occur in the film when the coating operation is performed by a coater or the like.
The method for imidizing the polyamic acid to form the adhesive polyimide is not particularly limited, and for example, a heat treatment such as heating at a temperature in the range of 80 to 400 ℃ for 0.1 to 24 hours can be suitably used.
Cross-linking formation of adhesive polyimide
In the case where the adhesive polyimide has a ketone group, a crosslinked structure can be formed by reacting the ketone group with an amino group of an amino compound having at least two primary amino groups as functional groups to form a c=n bond. By forming a crosslinked structure, heat resistance of the adhesive polyimide can be improved. As the tetracarboxylic anhydride preferable for forming the adhesive polyimide having a ketone group, for example, 3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) is exemplified, and as the diamine compound, for example, aromatic diamines such as 4,4' -bis (3-aminophenoxy) benzophenone (BABP), 1,3-bis [4- (3-aminophenoxy) benzoyl ] benzene (1, 3-bis [4- (3-aminophenoxy) benzoyl ] benzene, BABB) and the like are exemplified.
Examples of the amino compound that can be used for crosslinking of the adhesive polyimide include: dihydrazide compounds, aromatic diamines, aliphatic amines, and the like. Among these, dihydrazide compounds are preferable. Aliphatic amines other than dihydrazide compounds tend to form crosslinked structures even at room temperature, and there is concern about storage stability of varnishes, while aromatic diamines need to be set at high temperatures in order to form crosslinked structures. When the dihydrazide compound is used, both the storage stability of the varnish and the shortening of the curing time can be achieved. Examples of the dihydrazide compound include dihydrazide compounds such as oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, diglycolic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, 2, 6-naphthoic acid dihydrazide, 4-bisphenyldihydrazide, 1, 4-naphthoic acid dihydrazide, 2, 6-pyridine dihydrazide, itaconic acid dihydrazide and the like. The dihydrazide compounds mentioned above may be used alone or in combination of two or more.
When the adhesive polyimide is crosslinked, the amino compound is added to a resin solution containing the adhesive polyimide having a ketone group, and the ketone group in the adhesive polyimide and the primary amino group of the amino compound undergo a condensation reaction. The resin solution is cured by the condensation reaction to form a cured product. In this case, the amino compound may be added in such a manner that the total amount of the primary amino groups is 0.004 to 1.5 mol, preferably 0.005 to 1.2 mol, more preferably 0.03 to 0.9 mol, and most preferably 0.04 to 0.5 mol, based on 1 mol of the ketone group. If the total amount of the amino compounds is less than 0.004 mole based on 1 mole of the primary amino groups, the crosslinking of the adhesive polyimide using the amino compounds is insufficient, and therefore the heat resistance tends to be hardly exhibited in the adhesive layer BS after curing, and if the total amount of the amino compounds exceeds 1.5 mole based on 1 mole of the primary amino groups, the unreacted amino compounds act as a thermoplastic agent, and the heat resistance of the adhesive layer BS tends to be lowered.
The conditions for the condensation reaction for crosslinking are not particularly limited as long as the conditions for the formation of the imine bond (c=n bond) by the reaction of the ketone group in the adhesive polyimide with the primary amino group of the amino compound. The temperature of the thermal condensation is preferably in the range of 120 to 220 ℃, more preferably in the range of 140 to 200 ℃ for the reason that water produced by the condensation is discharged outside the system, or the condensation step is simplified when the thermal condensation reaction is performed after the synthesis of the adhesive polyimide. The reaction time is preferably about 30 minutes to 24 hours, and the end point of the reaction can be measured by, for example, infrared absorption spectroscopy using a Fourier transform infrared spectrophotometer (commercially available product: FT/IR620 manufactured by Japanese Spectroscopy), and using 1670cm -1 Near absorption peak reduction or disappearance of ketone group derived from polyimide resin and 1635cm -1 The occurrence of a nearby imide-derived absorption peak was confirmed.
The thermal condensation of the ketone group of the adhesive polyimide with the primary amino group of the amino compound can be carried out, for example, by the following method: (a) A method of adding an amino compound immediately after synthesis (imidization) of an adhesive polyimide and heating the mixture; (b) A method in which an excessive amount of an amino compound is previously charged as a diamine component, followed by synthesis (imidization) of an adhesive polyimide, and the remaining amino compound which does not participate in imidization or amidation is heated together with the adhesive polyimide; or (c) a method in which the composition of the adhesive polyimide to which the amino compound is added is processed into a predetermined shape and then heated (for example, after being applied to an arbitrary substrate or formed into a film shape).
The formation of the imine bond is described in the formation of the crosslinked structure in order to impart heat resistance to the adhesive polyimide, but the method is not limited thereto, and for example, epoxy resin curing agent, or the like may be blended and cured as a curing method of the adhesive polyimide.
[ Metal-clad laminate ]
The metal-clad laminate of the present embodiment includes a multilayer film 100, a multilayer film 101, and metal layers laminated on one or both surfaces of the multilayer film 100 and the multilayer film 101.
Fig. 3 shows a cross-sectional structure of a metal-clad laminate 200 according to a preferred embodiment of the present invention. The metal-clad laminate 200 has a structure in which a metal layer 110A and a metal layer 110B are laminated on both sides of a multilayer film 100. Therefore, the metal-clad laminate 200 has a structure in which the metal layer 110A/the first insulating resin layer 40A/the adhesive layer BS/the second insulating resin layer 40B/the metal layer 110B are laminated in this order. The metal layers 110A and 110B are located outermost, and the first insulating resin layer 40A and the second insulating resin layer 40B are disposed inside the metal layers, and the adhesive layer BS is interposed between the first insulating resin layer 40A and the second insulating resin layer 40B. The metal-clad laminate 200 having such a layer structure may be considered to have a structure in which a first single-sided metal-clad laminate (C1) in which the metal layer 110A, the thermoplastic polyimide layer 10A, and the non-thermoplastic polyimide layer 20A are laminated in this order, and a second single-sided metal-clad laminate (C2) in which the metal layer 110B, the thermoplastic polyimide layer 10B, and the non-thermoplastic polyimide layer 20B are laminated in this order are bonded to each other with the adhesive layer BS so that the insulating layer sides face each other.
Fig. 4 shows a cross-sectional structure of a metal-clad laminate 201 according to another preferred embodiment of the present invention. The metal-clad laminate 201 has a structure in which a metal layer 110A and a metal layer 110B are laminated on both sides of a multilayer film 101. Therefore, the metal-clad laminate 201 has a structure in which the metal layer 110A/the first insulating resin layer 40A/the adhesive layer BS/the second insulating resin layer 40B/the metal layer 110B are laminated in this order. The metal layers 110A and 110B are located outermost, and the first insulating resin layer 40A and the second insulating resin layer 40B are disposed inside the metal layers, and the adhesive layer BS is interposed between the first insulating resin layer 40A and the second insulating resin layer 40B. The metal-clad laminate 201 having such a layer structure may be considered to have a structure in which a first single-sided metal-clad laminate (C1) formed by stacking the metal layer 110A, the thermoplastic polyimide layer 10A, the non-thermoplastic polyimide layer 20A, and the thermoplastic polyimide layer 30A in this order, and a second single-sided metal-clad laminate (C2) formed by stacking the metal layer 110B, the thermoplastic polyimide layer 10B, the non-thermoplastic polyimide layer 20B, and the thermoplastic polyimide layer 30B in this order are bonded to each other with the adhesive layer BS so that the insulating layer sides face each other.
The material of the metal layer 110A and the metal layer 110B is not particularly limited, and examples thereof include: copper, stainless steel, iron, nickel, beryllium, aluminum, zinc, indium, silver, gold, tin, zirconium, tantalum, titanium, lead, magnesium, manganese, alloys thereof, and the like. Among them, copper or copper alloy is particularly preferable. The wiring layer in the circuit board according to the present embodiment described later is also made of the same material as the metal layer 110A and the metal layer 110B.
The thickness of the metal layers 110A and 110B is not particularly limited, and for example, in the case of using a metal foil such as a copper foil, it is preferably 35 μm or less, and more preferably in the range of 5 μm to 25 μm. The lower limit of the thickness of the metal foil is preferably set to 5 μm from the viewpoint of production stability and handling properties. In the case of using a copper foil, the copper foil may be a rolled copper foil or an electrolytic copper foil. Further, as the copper foil, a commercially available copper foil can be used.
For example, the metal foil may be subjected to surface treatment with a wallboard (bonding), an aluminum alkoxide, an aluminum chelate compound, a silane coupling agent, or the like for the purpose of improving the rust-proofing treatment or the adhesion.
When the metal-clad laminate 200 and the metal-clad laminate 201 are etched to remove the metal layers 110A and 110B, the dimensional change rate of the multilayer film 100 and 101 after etching is preferably within ±0.10% based on the multilayer film 100 and 101 before etching, and the dimensional change rate of the multilayer film 100 and 101 after etching is preferably within ±0.10% based on the multilayer film 100 and 101 after etching after heating at 150 ℃ for 30 minutes. The dimensional change rate of + -0.10% or less after etching and heating means that the dimensional change at the time of circuit processing is small, and the reliability of a circuit board such as FPC can be improved.
The dimensional change rate can be measured in the following order.
First, a 150mm square test piece made of a metal-clad laminate 200 and a metal-clad laminate 201 was used, and a dry film resist was exposed and developed at 100mm intervals to form a target for position measurement. After measuring the size before etching (normal state) in an environment with a temperature of 23+ -2deg.C and a relative humidity of 50+ -5%, copper other than the target material of the test piece was removed by etching (liquid temperature of 40 deg.C or less and time of 10 minutes or less). After standing at 23.+ -. 2 ℃ in an atmosphere having a relative humidity of 50.+ -. 5% for 24.+ -. 4 hours, the etched dimensions were measured. The dimensional change rates of the respective three points in the MD direction (longitudinal direction) and the TD direction (width direction) with respect to the normal state were calculated, and the average value of the dimensional change rates was used as the dimensional change rate after etching. The post-etching dimensional change rate can be calculated by the following equation.
Post-etching dimensional change ratio (%) = (B-ase:Sub>A)/a×100
A: spacing between targets prior to etching
B: spacing between etched targets
Next, the test piece was heat-treated in an oven at 150 ℃ for 30 minutes, and the distance between the targets at the subsequent positions was measured. The dimensional change rates of three points in the MD direction (longitudinal direction) and the TD direction (width direction) were calculated with respect to the etched dimensional change rates, and the average values of the three points were used as the dimensional change rates after the heat treatment. The dimensional change rate after heating can be calculated by the following equation.
Dimensional change after heating (%) = (C-B)/b×100
B: spacing between etched targets
C: distance between heated targets
[ production of Metal-clad laminate ]
The metal-clad laminate 200 and the metal-clad laminate 201 can be manufactured by, for example, the following method 1 or method 2. The adhesive polyimide to be the adhesive layer BS can be crosslinked as described above.
[ method 1]
First, a first single-sided metal-clad laminate (C1) and a second single-sided metal-clad laminate (C2) having the above-described layer structure are prepared. Next, the adhesive polyimide or a precursor thereof serving as the adhesive layer BS is formed into a sheet shape to prepare an adhesive sheet. The adhesive sheet is arranged between the first insulating resin layer 40A of the first single-sided metal-clad laminate (C1) and the second insulating resin layer 40B of the second single-sided metal-clad laminate (C2), and bonded thereto, and thermocompression bonding is performed.
[ method 2]
First, a first single-sided metal-clad laminate (C1) and a second single-sided metal-clad laminate (C2) are prepared. Next, a solution of the adhesive polyimide or a solution of a precursor thereof, which is the adhesive layer BS, is applied to one or both of the first insulating resin layer 40A of the first single-sided metal-clad laminate (C1) and the second insulating resin layer 40B of the second single-sided metal-clad laminate (C2) at a predetermined thickness, and dried to form a coating film. Then, the first single-sided metal-clad laminate (C1) and the second single-sided metal-clad laminate (C2) are bonded to each other on the coated film side, and thermocompression bonding is performed.
The first single-sided metal-clad laminate (C1) and the second single-sided metal-clad laminate (C2) used in the method 1 and the method 2 can be produced, for example, by: the metal foil to be the metal layer 110A and the metal layer 110B is repeatedly coated with a solution of polyamic acid, which is a precursor of thermoplastic polyimide or non-thermoplastic polyimide, and dried, and heat-treated to imidize.
The adhesive sheet used in the method 1 can be produced, for example, by the following method: (1) A method of coating a polyamic acid solution on an arbitrary support substrate, drying the solution, performing a heat treatment to imidize the solution, and then peeling the imidized solution from the support substrate to prepare an adhesive sheet; (2) A method in which a solution of a polyamic acid is applied to an arbitrary support substrate and dried, and then a gel film of the polyamic acid is peeled off from the support substrate, and the resultant is subjected to heat treatment and imidized to obtain an adhesive sheet; (3) And a method of forming an adhesive sheet by applying the solution of the adhesive polyimide onto a support substrate, drying the solution, and then peeling the dried solution from the support substrate.
In the above, the method of applying the polyimide solution (or the polyamic acid solution) to the metal foil, the support substrate, or the insulating resin layer is not particularly limited, and the polyimide solution may be applied by, for example, a doctor blade, a die, a knife, a die lip, or the like.
The metal-clad laminate 200 and the metal-clad laminate 201 of the present embodiment obtained as described above can be subjected to wiring circuit processing by etching or the like of the metal layer 110A and/or the metal layer 110B, and a circuit board such as a single-sided FPC or a double-sided FPC can be manufactured.
[ Circuit Board ]
The metal-clad laminate 200 and the metal-clad laminate 201 according to the present embodiment are mainly effective as circuit board materials such as FPCs and rigid-flexible circuit boards. That is, by patterning one or both of the two metal layers 110A and 110B of the metal-clad laminate 200 and the metal-clad laminate 201 according to the present embodiment by a conventional method to form a wiring layer, a circuit board such as an FPC according to an embodiment of the present invention can be manufactured.
Examples (example)
Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples. In the following examples, various measurements and evaluations are described below unless otherwise specified.
[ measurement of thermal expansion coefficient ]
A polyimide film having a size of 3mm X20 mm was heated from 30℃to 210℃at a constant temperature-rising rate at a constant temperature-rising rate while applying a load of 5.0g, and then kept at that temperature for 10 minutes, and then cooled at a rate of 5℃to 100℃for an average thermal expansion coefficient (thermal expansion coefficient) of 200℃to 100℃using TMA (trade name: TMA/SS6000, manufactured by Hitachi High-Tech).
[ measurement of storage modulus of elasticity ]
A dynamic viscoelasticity measuring apparatus (DMA: manufactured by Japanese TA instruments (TA Instruments Japan) Co., ltd., trade name: RSA-G2) was used for a sample film having a size of 5mm X20 mm, and the measurement was performed at a temperature rising rate of 10 ℃/min and a frequency of 1Hz from 25℃to 300 ℃. The temperature at which the change in the elastic modulus (tan δ) is the maximum is set as the glass transition temperature.
[ measurement of relative permittivity and dielectric loss tangent ]
The relative dielectric constant (Dk) and dielectric loss tangent (Df) of the resin sheet at 20GHz were measured using a vector network analyzer (Vector Network Analyzer) (manufactured by Agilent, trade name: E8363C) and an SPDR resonator. In addition, the materials used in the assay are at temperature: 24-26 ℃ and humidity: the material is left for 24 hours at 45% to 55% relative humidity (Relative Humidity, RH).
[ measurement of viscosity ]
The viscosity at 25℃was measured using an E-type viscometer (trade name: DV-II+Pro, manufactured by Brookfield Co.). The rotational speed was set so that the torque (torque) became 10% to 90%, and after 2 minutes passed since the start of measurement, the value at which the viscosity was stable was read.
[ measurement of weight average molecular weight (Mw) ]
The weight average molecular weight was measured by gel permeation chromatograph (Gel Permeation Chromatograph) (HLC-8220 GPC, manufactured by Tosoh Co., ltd.). Polystyrene was used as a standard substance, and Tetrahydrofuran (THF) was used as a developing solvent
[ measurement of dimensional Change Rate after etching ]
First, a 150mm square test piece made of a metal-clad laminate was used, and the dry film resist was exposed and developed at 100mm intervals to form a target for position measurement. After measuring the size before etching (normal state) in an environment with a temperature of 23+ -2deg.C and a relative humidity of 50+ -5%, copper other than the target material of the test piece was removed by etching (liquid temperature of 40 deg.C or less and time of 10 minutes or less). After standing at 23.+ -. 2 ℃ in an atmosphere having a relative humidity of 50.+ -. 5% for 24.+ -. 4 hours, the etched dimensions were measured. The dimensional change rates of the respective three points in the MD direction (longitudinal direction) and the TD direction (width direction) with respect to the normal state were calculated, and the average value of the dimensional change rates was used as the dimensional change rate after etching. The post-etching dimensional change rate can be calculated by the following equation.
Post-etching dimensional change ratio (%) = (B-ase:Sub>A)/a×100
A: spacing between targets prior to etching
B: spacing between etched targets
[ measurement of dimensional Change Rate after heating ]
Next, the test piece, on which the dimensional change rate after etching was measured, was heat-treated in an oven at 150 ℃ for 30 minutes, and the distance between the targets at the subsequent positions was measured. The dimensional change rates of three points in the MD direction (longitudinal direction) and the TD direction (width direction) were calculated with respect to the etched dimensional change rates, and the average values of the three points were used as the dimensional change rates after the heat treatment. The dimensional change rate after heating can be calculated by the following equation.
Dimensional change after heating (%) = (C-B)/b×100
B: spacing between etched targets
C: distance between heated targets
[ measurement of peel Strength ]
The copper foil on the copper-clad laminate sample was subjected to circuit processing to form lines and spaces having a width of 1.0mm and an interval of 5.0mm, and then cut into pieces: the measurement sample was prepared with a width of 8 cm. Times.4 cm. A Tensilon tester (Tensilon tester) (manufactured by Toyo Seisaku machine, trade name: stokes Lav (Stroggraph) VE-1D), the resin layer side of the measurement sample was fixed to an aluminum plate by a double-sided tape, and the copper foil was peeled at a speed of 50 mm/min in the 180℃direction, and the center strength of the copper foil when peeled 10mm from the resin layer was determined.
Abbreviations used in this example represent the following compounds.
BPDA:3,3', 4' -biphenyltetracarboxylic dianhydride
PMDA: pyromellitic dianhydride
m-TB:2,2 '-dimethyl-4, 4' -diaminobiphenyl
TPE-R:1, 3-bis (4-aminophenoxy) benzene
bis-aniline-M: 1, 3-bis [2- (4-aminophenyl) -2-propyl ] benzene
NMP: n-methyl-2-pyrrolidone
DMAc: n, N-dimethylacetamide
BTDA:3,3', 4' -benzophenone tetracarboxylic dianhydride
DDA: aliphatic diamine having 36 carbon atoms (manufactured by Croda Japan, trade name: priamine 1074, amine number: 205mgKOH/g, mixture of dimer diamine having cyclic structure and chain structure, dimer component content: 95% by weight or more)
BAPP:2, 2-bis [4- (4-aminophenoxy) phenyl ] propane
N-12: dodecanedioic acid dihydrazide
OP935: aluminum organic phosphonate (trade name: ai Kesuo Lite (Exolit) OP935 manufactured by Clariant Japan Co., ltd.)
Polystyrene elastomer: manufactured by KRATON (KRATON), trade name: MD1653MO (hydrogenated polystyrene elastomer, styrene unit content: 30% by weight, mw:80,499, acid value-free)
Synthesis example 1
Preparation of polyamic acid solution for insulating resin layer
Under a nitrogen stream, 69.56g of m-TB (0.328 mol), 542.75g of TPE-R (1.857 mol) and DMAc having a solid content concentration of 12% by weight after polymerization were charged into the reaction vessel, and dissolved by stirring at room temperature. Next, 194.39g of PMDA (0.891 mol) and 393.31g of BPDA (1.337 mol) were added, and the mixture was stirred at room temperature for 3 hours to carry out polymerization, thereby obtaining a polyamic acid solution 1 (viscosity: 2,700 mPa. Multidot.s).
The polyimide film produced using the polyamic acid solution 1 had a storage modulus of elasticity of 4.3X10 at 30 ℃ 9 Pa, at 300℃is 9.4X10) 7 Pa, is thermoplastic.
Synthesis example 2
Preparation of polyamic acid solution for insulating resin layer
Under a nitrogen stream, 64.20g of M-TB (0.302 mol) and 5.48g of bisaniline-M (0.016 mol) and DMAc having a solid content concentration of 15% by weight after the polymerization were charged into the reaction vessel, and dissolved by stirring at room temperature. Next, 34.20g of PMDA (0.157 mol) and 46.13g of BPDA (0.157 mol) were added, and the mixture was stirred at room temperature for 3 hours to carry out polymerization, thereby obtaining a polyamic acid solution 2 (viscosity: 28,000 mPas).
Polyimide film produced using polyamic acid solution 2 has storage elastic modulus at 30 DEG C Is 7.0X10 9 Pa, at 300℃is 5.4X10) 8 Pa, is non-thermoplastic.
Synthesis example 3
Preparation of resin solution for adhesive layer
A500 ml separable flask was charged with 21.34g of BTDA (0.06622 mol), 12.99g of BPDA (0.04414 mol), 46.7042g of DDA (0.08741 mol), 8.97104g of BAPP (0.02185 mol), 126g of NMP and 84g of xylene, and the materials were thoroughly mixed at 40℃for 1 hour to prepare a polyamic acid solution. The polyamic acid solution was heated to 190℃and stirred for 5 hours, and 65g of xylene was added to prepare an imidized polyimide solution 1 (solid content: 31% by weight, weight average molecular weight: 35,886, viscosity: 2,580 mPa.s).
Production example 1
Preparation of resin sheet for adhesive layer
To 40.97g (12.7 g as a solid content) of polyimide solution 1 were blended 0.46g of N-12, 2.54g of OP935, and 7.62g of polystyrene elastomer resin, and 45.23g of xylene was added to dilute the mixture, thereby preparing polyimide varnish 1.
The polyimide varnish 1 was applied to the silicone-treated surface of a release substrate (length×width×thickness=320 mm×240mm×25 μm) so that the thickness thereof became 50 μm after drying, and then dried by heating at 80 ℃ for 15 minutes, followed by peeling from the release substrate, whereby a resin sheet 1 was produced. The storage modulus of elasticity of the resin sheet 1 is as follows.
Storage modulus of elasticity (25 ℃ C.). 901MPa
Storage modulus of elasticity (100 ℃ C.). 5.0MPa
Storage modulus of elasticity (200 ℃ C.). 2.0MPa
Production example 2
Preparation of single-sided metal-clad laminate
The polyamic acid solution 1 was uniformly applied to the copper foil 1 (electrolytic copper foil, thickness: 12 μm, surface roughness Rz on the resin layer side: 0.6 μm) so that the thickness after curing was about 1.6 μm, and then dried by heating at 120℃to remove the solvent. Next, the polyamic acid solution 2 was uniformly applied thereto so that the thickness after curing was about 2.4 μm, and then heated and dried at 120 ℃ to remove the solvent. Further, the single-sided metal clad laminate 1 was prepared by performing stepwise heat treatment from 120 ℃ to 360 ℃ to complete imidization.
Production examples 3 to 4
A single-sided metal-clad laminate 2 and a single-sided metal-clad laminate 3 were produced in the same manner as in production example 2, except that the thicknesses of the polyamic acid solution 1 and the polyamic acid solution 2 after curing were changed as shown in table 1.
TABLE 1
Production example 5
The polyamic acid solution 1 was uniformly applied to the copper foil 1 so that the thickness thereof after curing was about 2 μm, and then dried by heating at 120℃to remove the solvent. Next, the polyamic acid solution 2 was uniformly applied thereto so that the thickness after curing was about 21 μm, and then heated and dried at 120 ℃ to remove the solvent. Further, the polyamic acid solution 1 was uniformly applied thereto so that the thickness after curing was about 2. Mu.m, and then dried by heating at 120℃to remove the solvent. Further, the single-sided metal clad laminate 4 was prepared by performing stepwise heat treatment from 120 to 360 ℃.
Preparation of polyimide film
The copper foil layers of the single-sided metal clad laminate 1 to the single-sided metal clad laminate 4 were removed by etching using an aqueous solution of ferric chloride to prepare polyimide films 1 to 4. The thermal expansion coefficient and the storage elastic coefficient of the polyimide layer were measured using the polyimide films 1 to 4 thus prepared. The results are shown in Table 2 or Table 3.
Example 1
The polyimide varnish 1 was applied to the insulating resin layer side surface of the single-sided metal clad laminate 1 so as to have a thickness of 46 μm after drying, and then dried by a stepwise heat treatment from 80 to 200 ℃. Two of the single-sided metal clad laminate plates 1 with adhesive layers were prepared, the adhesive layer sides were laminated together, and pressure of 3.5MPa was applied at 180 ℃ for 2 hours for pressure bonding, to prepare a metal clad laminate plate 1. Further, the copper foil layer in the metal-clad laminate 1 was etched away to obtain a multilayer film 1. The dimensional change rate and peel strength were measured using the metal-clad laminate 1, and the dielectric characteristics and thermal expansion coefficient were measured using the multilayer film 1.
Examples 2 to 3
A metal-clad laminate 2 to a metal-clad laminate 3 and a multilayer film 2 to a multilayer film 3 were produced in the same manner as in example 1 except that the thickness of the polyimide varnish 1 after drying was changed to 37.5 μm and the single-sided metal-clad laminate 1 was changed to a single-sided metal-clad laminate 2 and a single-sided metal-clad laminate 3.
The layer structures and evaluation results of the produced metal-clad laminated plates 1 to 3 and the multilayer films 1 to 3 are shown in table 2. In table 2, the total thickness of the thermoplastic polyimide layers is set to T A The total thickness of the non-thermoplastic polyimide layers is set as T B The thickness of the adhesive layer was tad.
TABLE 2
Comparative example 1
A fluororesin sheet 1 (trade name: adhesive perfluoro resin EA-2000 manufactured by asahi corporation) having a thickness of 50 μm and a thickness of 25 μm and two single-sided metal-clad laminate plates 2 were prepared, and the two fluororesin sheets were laminated with being sandwiched between the insulating resin layer sides of the two single-sided metal-clad laminate plates 2, and were pressure-bonded at 320 ℃ for 5 minutes under a pressure of 3.5MPa, to prepare a metal-clad laminate plate 4. The evaluation results of the metal-clad laminate 4 and the multilayer film 4 after copper foil removal are shown in table 3.
Comparative example 2
Two single-sided metal clad laminate plates 4 were prepared, and the respective insulating resin layer side surfaces were overlapped with the two surfaces of the resin sheet 1, and the metal clad laminate plates 5 were prepared by pressure bonding at 180 ℃ under a pressure of 3.5MPa for 2 hours. The evaluation results of the metal-clad laminate 5 and the multilayer film 5 after copper foil removal are shown in table 3.
Comparative example 3
A metal-clad laminate 6 was produced in the same manner as in comparative example 2, except that the fluororesin sheet 1 was used instead of the resin sheet 1 and the pressure of 3.5MPa was applied at 320 ℃ for 5 minutes. The evaluation results of the metal-clad laminate 6 and the multilayer film 6 after copper foil removal are shown in table 3.
TABLE 3
Comparing comparative example 1 with comparative example 3, it is found that the dimensional stability is significantly deteriorated as the thickness of the polyimide layer of the outer layer is reduced in the case of the structure in which the storage modulus of elasticity is high at high temperature of the inner layer. In addition, when comparing comparative example 1 with example 2, it is found that the dimensional stability is further deteriorated when the adhesive layer having low elasticity is used at normal temperature, and it is important to use the storage modulus of elasticity at a process temperature range rather than normal temperature in order to secure the dimensional stability.
As a result, in the structure in which the size control layer is provided on the outer layer and the low dielectric layer is provided on the inner layer, it is important to control the thickness balance of each layer and the storage modulus of elasticity of the process temperature zone of the inner layer within a predetermined range in order to reduce the thickness of the outer layer.
Specifically, an index (P) calculated from the storage elastic modulus and thickness at 100℃and 200℃can be used P /P AD ). In comparative example 1, due to P P /P AD Too small, the effect of the adhesive layer is strongly exhibited, and the size deteriorates. In order to secure sufficient dimensional stability, it is necessary to set the ratio of (P) to be equal to or higher than that of comparative example 3 and example 1 P /P AD ). In addition, in the same manner as in comparative example 2 (P P /P AD ) If the thickness is too high, the polyimide layer is too thick, and thus the dielectric characteristics are deteriorated, although the dimensional stability is ensured.
Reference example 1
The polyamic acid solution 1 was uniformly applied to the copper foil 1 so that the thickness thereof after curing was about 0.8 μm, and then dried by heating at 120℃to remove the solvent. Next, the polyamic acid solution 2 was uniformly applied thereto so that the thickness after curing was about 2.9 μm, and then heated and dried at 120 ℃ to remove the solvent. Further, the polyamic acid solution 1 was uniformly applied thereto so that the thickness after curing was about 0.8. Mu.m, and then dried by heating at 120℃to remove the solvent. Further, the single-sided metal clad laminate 5 was prepared by performing stepwise heat treatment from 120 to 360 ℃. The peel strength of the single-sided metal-clad laminate 5 was measured and found to be 0.6kN/m.
In both comparative example 2 and example 1, the CTE of the polyimide layer was in a preferable range of about 20ppm/K, but ratio of thermoplastic polyimide layer to non-thermoplastic polyimide layer (T A )/(T A +T B ) Are quite different. In the case of forming a polyimide layer by a casting method, since CTE is reduced as the thickness is reduced, it is necessary to apply (T A )/(T A +T B ) The inhibition is within a prescribed range.
In addition, as in reference example 1, when the polyimide layer is thinned in a state where the thermoplastic polyimide is held in two layers and the non-thermoplastic polyimide is one layer in the conventional design, the peel strength is lowered. On the other hand, in the design in which the thermoplastic polyimide layer is concentrated on the substrate side and the outer layer portion has a one-sided two-layer structure as in example 1, sufficient peel strength is exhibited. Therefore, in the design of thinning the polyimide layer, a two-layer structure of thermoplastic polyimide and non-thermoplastic polyimide is effective from the viewpoint of adhesion to the copper foil.
Although the embodiments of the present invention have been described in detail for the purpose of illustration, the present invention is not limited to the embodiments, and various modifications are possible.
Claims (14)
1. A multilayer film comprising a plurality of polyimide layers and an adhesive layer, the multilayer film having a layer structure of (1) or (2) below:
(1) Thermoplastic polyimide layer/non-thermoplastic polyimide layer/adhesive layer/non-thermoplastic polyimide layer/thermoplastic polyimide layer,
or,
(2) Thermoplastic polyimide layer/non-thermoplastic polyimide layer/adhesive layer/thermoplastic polyimide layer/non-thermoplastic polyimide layer/thermoplastic polyimide layer, and
Satisfying the following conditions a) to c):
a) The total thickness of the thermoplastic polyimide layer and the non-thermoplastic polyimide layer laminated on one side of the adhesive layer is in the range of 2 μm to 20 μm;
b) Satisfying the following formula (i);
65＜P P /P AD ＜1,550…(i)
here, P P Is the elasticity coefficient parameter of the polyimide layer, P AD The elastic coefficient parameter of the adhesive layer is represented by the following formulas (ii) to (v):
P P ＝P P1 +P P2 …(ii)
P P1 ＝(E' P100 +E' P200 )×t p1 …(iii)
P P2 ＝(E' P100 +E' P200 )×t p2 …(iv)
P AD ＝(E' AD100 +E' AD200 )×tad…(v)
E' P100 : storage elastic coefficient [ GPa ] of polyimide layer at 100 DEG C]
E' P200 : storage elastic coefficient [ GPa ] of polyimide layer at 200 DEG C]
E' AD100 : storage elastic coefficient [ GPa ] of adhesive layer at 100deg.C]
E' AD200 : storage elastic coefficient [ GPa ] of adhesive layer at 200 DEG C]
t p1 : total thickness [ μm ] of thermoplastic polyimide layer and non-thermoplastic polyimide layer laminated on one side of adhesive layer]
t p2 : total thickness [ μm ] of thermoplastic polyimide layer and non-thermoplastic polyimide layer laminated on the other side of the adhesive layer]
tad: thickness of adhesive layer [ mu ] m
Here, the coefficient of elasticity parameter P of the polyimide layer P To make the elastic coefficient parameter P P1 And coefficient of elasticity parameter P P2 The value obtained by addition, the coefficient of elasticity parameter P P1 The elastic modulus parameter P is calculated by the formula (iii) by taking the thermoplastic polyimide layer and the non-thermoplastic polyimide layer laminated on one side of the adhesive layer as one polyimide layer P2 The thermoplastic polyimide layer and the non-thermoplastic polyimide layer laminated on the other side of the adhesive layer are calculated by the formula (iv) with the thermoplastic polyimide layer and the non-thermoplastic polyimide layer being regarded as one polyimide layer,
c) The dielectric loss tangent at 20GHz measured by using a separation column dielectric resonator is less than 0.0029 as the whole of the multilayer film.
2. The multilayer film according to claim 1, wherein the polyimide layer obtained by laminating a thermoplastic polyimide layer laminated on one side of the adhesive layer and a non-thermoplastic polyimide has a storage elastic modulus of 1.0GPa or more at 100 ℃ and a storage elastic modulus of 0.1GPa or more at 200 ℃.
3. The multilayer film according to claim 1, wherein the adhesive layer has a storage elastic modulus at 100 ℃ of less than 130MPa and a storage elastic modulus at 200 ℃ of 40MPa or less.
4. The multilayer film according to claim 1, wherein the total thickness of the thermoplastic polyimide layers in the entire multilayer film is T A The total thickness of the non-thermoplastic polyimide layers is set as T B When the thickness of the adhesive layer is tad, the following formula (vi) is satisfied:
0.60≦tad/(T A +T B +tad)≦0.99…(vi)。
5. the multilayer film according to claim 1, wherein the polyimide layer obtained by laminating a thermoplastic polyimide layer laminated on one side of the adhesive layer and a non-thermoplastic polyimide layer has a thermal expansion coefficient in the range of 5ppm/K to 35 ppm/K.
6. The multilayer film according to claim 1, wherein the adhesive layer contains thermoplastic polyimide and polystyrene elastomer resin, and the content of the polystyrene elastomer resin is in a range of 10 parts by weight to 150 parts by weight with respect to 100 parts by weight of the thermoplastic polyimide.
7. The multilayer film according to claim 6, wherein the thermoplastic polyimide contained in the adhesive layer contains an acid dianhydride residue derived from an acid dianhydride component and a diamine residue derived from a diamine component, and the content of diamine residues derived from a dimer diamine composition containing a dimer diamine in which two terminal carboxylic acid groups of dimer acid are substituted with primary aminomethyl groups or amino groups as a main component is 20 mol% or more based on the total diamine residues, and the content of diamine residues derived from a diamine compound represented by the following general formula (1) is 5 mol% to 50 mol% in total,
in formula (1), R independently represents a halogen atom, or an alkyl or alkoxy group which may be substituted with a halogen atom of 1 to 6 carbon atoms, or a phenyl or phenoxy group which may be substituted with a monovalent hydrocarbon group of 1 to 6 carbon atoms, Z independently represents a group selected from the group consisting of-O-, -S-, -CH 2 -、-CH(CH 3 )-、-C(CH 3 ) 2 -、-CO-、-COO-、-SO 2 Divalent radical-NH-or-NHCO-, m 1 Independently represents an integer of 0 to 4, m 2 And represents an integer of 0 to 2.
8. The multilayer film according to claim 6, wherein the thermoplastic polyimide contained in the adhesive layer is a crosslinked polyimide in which a ketone group contained in a molecular chain and an amino group of an amino compound having at least two primary amino groups as functional groups form a crosslinked structure through a c=n bond.
9. The multilayer film according to claim 1, wherein the thermoplastic polyimide constituting the thermoplastic polyimide layer contains an acid dianhydride residue derived from an acid dianhydride component and a diamine residue derived from a diamine component, and the proportion of 3,3', 4' -biphenyl tetracarboxylic acid dianhydride residues derived from 3,3', 4' -biphenyl tetracarboxylic acid dianhydride relative to the total acid dianhydride residues is 40 mol% or more, and the proportion of diamine residues derived from a diamine compound represented by the following general formula (1) relative to the total diamine residues is 30 mol% or more,
in formula (1), R independently represents a halogen atom, or an alkyl or alkoxy group which may be substituted with a halogen atom of 1 to 6 carbon atoms, or a phenyl or phenoxy group which may be substituted with a monovalent hydrocarbon group of 1 to 6 carbon atoms, Z independently represents a group selected from the group consisting of-O-, -S-, -CH 2 -、-CH(CH 3 )-、-C(CH 3 ) 2 -、-CO-、-COO-、-SO 2 Divalent radical-NH-or-NHCO-, m 1 Independently represents an integer of 0 to 4, m 2 And represents an integer of 0 to 2.
10. The multilayer film according to claim 1, wherein the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer contains an acid dianhydride residue derived from an acid dianhydride component and a diamine residue derived from a diamine component, and the proportion of the acid dianhydride residue having a biphenyl skeleton with respect to all the acid dianhydride residues is 40 mol% or more, and the proportion of the diamine residue having a biphenyl skeleton with respect to all the diamine residues is 40 mol% or more.
11. A metal-clad laminate having the multilayer film according to any one of claims 1 to 10, and a metal layer laminated on one or both sides of the multilayer film.
12. The metal-clad laminate according to claim 11, wherein when the metal layer is etched and removed, a dimensional change rate of the etched multilayer film is within ±0.10% based on the multilayer film before etching, and a dimensional change rate of the etched multilayer film is within ±0.10% after heating at 150 ℃ for 30 minutes based on the etched multilayer film.
13. A circuit board comprising the metal layer of the metal-clad laminate according to claim 11 processed into wiring.
14. A circuit board comprising an insulating resin layer and a wiring layer provided on at least one surface of the insulating resin layer, wherein, in the circuit board,
the insulating resin layer is the multilayer film according to any one of claims 1 to 10.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022044835A JP2023139352A (en) | 2022-03-22 | 2022-03-22 | Multilayer film, metal-clad laminate and circuit board |
| JP2022-044834 | 2022-03-22 | ||
| JP2022-044835 | 2022-03-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116787887A true CN116787887A (en) | 2023-09-22 |
Family
ID=88036922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310223489.8A Pending CN116787887A (en) | 2022-03-22 | 2023-03-09 | Multilayer film, metal-clad laminate, and circuit board |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2023139352A (en) |
| CN (1) | CN116787887A (en) |
-
2022
- 2022-03-22 JP JP2022044835A patent/JP2023139352A/en active Pending
-
2023
- 2023-03-09 CN CN202310223489.8A patent/CN116787887A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JP2023139352A (en) | 2023-10-04 |
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