WO2022014257A1 - Film de polyimide multicouche - Google Patents

Film de polyimide multicouche Download PDF

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Publication number
WO2022014257A1
WO2022014257A1 PCT/JP2021/023195 JP2021023195W WO2022014257A1 WO 2022014257 A1 WO2022014257 A1 WO 2022014257A1 JP 2021023195 W JP2021023195 W JP 2021023195W WO 2022014257 A1 WO2022014257 A1 WO 2022014257A1
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residue
thermoplastic polyimide
flask
layer
thermoplastic
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PCT/JP2021/023195
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English (en)
Japanese (ja)
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隆宏 秋永
隼平 齋藤
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株式会社カネカ
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Priority to KR1020237005185A priority Critical patent/KR20230038757A/ko
Priority to JP2022536190A priority patent/JPWO2022014257A1/ja
Priority to CN202180060432.XA priority patent/CN116133855A/zh
Publication of WO2022014257A1 publication Critical patent/WO2022014257A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the present invention relates to a multi-layer polyimide film.
  • FPC flexible printed wiring boards
  • a flexible printed wiring board using a multi-layer polyimide film containing a thermoplastic polyimide layer as an adhesive layer is expected to further increase in demand because of its excellent heat resistance and flexibility.
  • electronic devices have been made lighter, smaller, and thinner, and there is still a strong demand for miniaturization of FPC wiring.
  • a metal-clad laminate in which a metal foil such as a copper foil is laminated on both sides of a polyimide film.
  • FPC manufacturing there is a step of first drilling a hole (hereinafter, may be referred to as “via”) for conducting conduction between layers.
  • via By plating the inner wall of the via, both sides of the wiring board can be made conductive.
  • a through-hole method is used to make through holes in the metal foil and insulating layer (polygonite layer) on both sides with a drill or laser, and the metal foil and insulating layer on one side are cut with a laser or the like, and the other is used.
  • a blind via method that leaves the metal leaf on the surface of the surface, but the blind via method is frequently used in order to effectively use the area, especially in the fine FPC.
  • Patent Document 1 describes a method of adding a heat treatment step between laser processing and desmear processing to remove residual stress generated by laser processing and suppress the generation of defects.
  • Patent Document 2 discloses a polyimide having resistance to an alkaline solution used in a developing step, an etching treatment step, and a resist stripping step.
  • Patent Document 1 If a method of adding a heat treatment step between laser processing and desmear processing as disclosed in Patent Document 1 is adopted as a method for suppressing the occurrence of cracks, the heat treatment process is separately increased, so that the production of the wiring board is performed. It causes a decrease in sex. Further, the method described in Patent Document 1 has room for improvement in suppressing the occurrence of cracks on the inner wall of the via.
  • Patent Document 2 can suppress the tearing of the film in an alkaline environment, there is still room for improvement in suppressing the occurrence of cracks on the inner wall of the via.
  • the present invention has been made in view of these problems, and an object of the present invention is to provide a multi-layer polyimide film capable of suppressing the occurrence of cracks on the inner wall of a via during desmear treatment after laser processing.
  • the multilayer polyimide film according to the present invention has a non-thermoplastic polyimide layer and a thermoplastic polyimide layer arranged on at least one side of the non-thermoplastic polyimide layer.
  • the non-thermoplastic polyimide contained in the non-thermoplastic polyimide layer has a tetracarboxylic dianhydride residue and a diamine residue.
  • the diamine residue includes a diamine residue having a biphenyl skeleton, a 4,4'-diaminodiphenyl ether residue, and a p-phenylenediamine residue.
  • the content of the diamine residue having the biphenyl skeleton is 20 mol% or more and 35 mol% or less with respect to the total diamine residue constituting the non-thermoplastic polyimide.
  • the diamine residue having the biphenyl skeleton is a 4,4'-diamino-2,2'-dimethylbiphenyl residue.
  • the content of the 4,4'-diaminodiphenyl ether residue is 40 mol% or more 70 with respect to the total diamine residue constituting the non-thermoplastic polyimide. It is less than mol%.
  • the content of the p-phenylenediamine residue is 5 mol% or more and 50 mol% or less with respect to all the diamine residues constituting the non-thermoplastic polyimide. Is.
  • the tetracarboxylic acid dianhydride residue is 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride residue and pyromellitic acid dianhydride residue. Includes one or more selected from the group consisting of substance residues.
  • the tetracarboxylic acid dianhydride residue further contains 4,4'-oxydiphthalic acid anhydride residue.
  • the content of the 4,4'-oxydiphthalic acid anhydride residue is relative to the total tetracarboxylic acid dianhydride residue constituting the non-thermoplastic polyimide. It is 5 mol% or more and 15 mol% or less.
  • the thermoplastic polyimide contained in the thermoplastic polyimide layer is a 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride residue and pyromellitic acid. It has one or more selected from the group consisting of dianhydride residues and 2,2-bis [4- (4-aminophenoxy) phenyl] propane residues.
  • the storage elastic modulus of the non-thermoplastic polyimide layer at a temperature of 380 ° C. is less than 0.350 GPa.
  • the coefficient of linear expansion when the temperature rises from 100 ° C. to 200 ° C. of the non-thermoplastic polyimide layer is 5.0 ppm / K or more and 19.0 ppm / K or less. ..
  • the multilayer polyimide film according to the present invention it is possible to suppress the occurrence of cracks on the inner wall of the via during the desmear treatment after the laser processing without increasing the man-hours in the manufacturing process of the wiring board.
  • Polyimide is a polymer having a structural unit represented by the following general formula (1) as a repeating unit.
  • X represents a tetracarboxylic acid dianhydride residue (a tetravalent organic group derived from a tetracarboxylic acid dianhydride), and Y represents a diamine residue (a divalent organic derived from a diamine). Represents the group).
  • Biphenyl skeleton refers to a bicyclic skeleton in which two benzene rings are bonded by one single bond. Therefore, the diamine residue having a biphenyl skeleton does not include the diamine residue having a condensed ring such as the 9,9-bis (4-aminophenyl) fluorene residue.
  • linear expansion coefficient is, unless otherwise specified, the linear expansion coefficient at the time of temperature rise from 100 ° C to 200 ° C.
  • Non-thermoplastic polyimide is a film shape (flat) that does not wrinkle or stretch when fixed to a metal fixing frame and heated at a heating temperature of 450 ° C for 2 minutes. A polyimide that retains the film shape).
  • the "thermoplastic polyimide” refers to a polyimide that does not retain its film shape when fixed to a metal fixing frame in a film state and heated at a heating temperature of 450 ° C. for 2 minutes.
  • the "main surface" of a layered material refers to a surface orthogonal to the thickness direction of the layered material.
  • the multilayer polyimide film according to the present embodiment has a non-thermoplastic polyimide layer and a thermoplastic polyimide layer arranged on at least one side (one main surface) of the non-thermoplastic polyimide layer.
  • the non-thermoplastic polyimide contained in the non-thermoplastic polyimide layer has a tetracarboxylic dianhydride residue and a diamine residue.
  • the diamine residue includes a diamine residue having a biphenyl skeleton (a residue derived from a diamine having a biphenyl skeleton), a 4,4'-diaminodiphenyl ether residue, and a p-phenylenediamine residue.
  • the content of diamine residues having a biphenyl skeleton is preferably 20 mol% or more and 35 mol% or less with respect to all the diamine residues constituting the non-thermoplastic polyimide.
  • the tetracarboxylic dianhydride may be referred to as "acid dianhydride".
  • a diamine having a biphenyl skeleton may be referred to as "BPDI”.
  • 4,4'-diaminodiphenyl ether may be referred to as "ODA”.
  • P-phenylenediamine may be referred to as "PDA”.
  • the non-thermoplastic polyimide contained in the non-thermoplastic polyimide layer may be simply referred to as "non-thermoplastic polyimide”.
  • the thermoplastic polyimide contained in the thermoplastic polyimide layer may be simply referred to as "thermoplastic polyimide”.
  • the present inventors have diligently studied the molecular design of polyimide that can relieve the stress generated in the film during laser processing while maintaining the heat resistance (linear expansion coefficient, etc.) when used for a metal-clad laminate. As a result, the present inventors have optimized the structure of the non-thermoplastic polyimide contained in the multi-layer polyimide film, so that the desmear treatment after laser processing can be performed without significantly changing the manufacturing process of the wiring board. It was found that the occurrence of cracks on the inner wall of the via can be suppressed.
  • FIG. 1 is a cross-sectional view showing an example of a multi-layer polyimide film according to this embodiment.
  • the multilayer polyimide film 10 has a non-thermoplastic polyimide layer 11 and a thermoplastic polyimide layer 12 arranged on at least one side of the non-thermoplastic polyimide layer 11.
  • the non-thermoplastic polyimide contained in the non-thermoplastic polyimide layer 11 has a tetracarboxylic dianhydride residue and a diamine residue.
  • Diamine residues include BPDI residues, ODA residues, and PDA residues.
  • the content of the BPDI residue is preferably 20 mol% or more and 35 mol% or less with respect to all the diamine residues constituting the non-thermoplastic polyimide contained in the non-thermoplastic polyimide layer 11.
  • the multi-layer polyimide film 10 it is possible to suppress the occurrence of cracks on the inner wall of the via during the desmear treatment after laser processing.
  • the reason is presumed as follows.
  • the non-thermoplastic polyimide contained in the non-thermoplastic polyimide layer 11 has a BPDI residue containing a skeleton having a high degree of free rotation of the molecular chain in a specific range.
  • the non-thermoplastic polyimide contained in the non-thermoplastic polyimide layer 11 has a bent structure ODA residue that contributes to the flexibility of the multi-layer polyimide film 10 and a rigid structure that contributes to the heat resistance of the multi-layer polyimide film 10. It has a PDA residue.
  • the multilayer polyimide film 10 can relieve the stress generated in the film during laser processing while maintaining the heat resistance (linear expansion coefficient and the like) when used for the metal-clad laminate. Therefore, according to the multi-layer polyimide film 10, it is possible to suppress the occurrence of cracks on the inner wall of the via during the desmear treatment after the laser processing.
  • the benzene ring in the BPDI residue preferably has a substituent, more preferably an alkyl group, and methyl. It is more preferable to have a group.
  • thermoplastic polyimide layer 12 is provided only on one side of the non-thermoplastic polyimide layer 11, but heat is generated on both surfaces (both main surfaces) of the non-thermoplastic polyimide layer 11.
  • the plastic polyimide layer 12 may be provided.
  • the two-layer thermoplastic polyimide layer 12 may contain the same type of thermoplastic polyimide, and different types of thermoplastic polyimides may be contained. May include. Further, the thicknesses of the two thermoplastic polyimide layers 12 may be the same or different.
  • both the non-thermoplastic polyimide layer 11 and the thermoplastic polyimide layer 12 may be provided in two or more layers.
  • the "multi-layer polyimide film 10" includes a film in which the thermoplastic polyimide layer 12 is provided on only one side of the non-thermoplastic polyimide layer 11 and a thermoplastic polyimide on both sides of the non-thermoplastic polyimide layer 11.
  • a film provided with the layer 12 and a film provided with two or more layers of both the non-thermoplastic polyimide layer 11 and the thermoplastic polyimide layer 12 are included.
  • the thickness of the multilayer polyimide film 10 (total thickness of each layer) is, for example, 6 ⁇ m or more and 60 ⁇ m or less.
  • the thickness of the multilayer polyimide film 10 is preferably 7 ⁇ m or more and 30 ⁇ m or less, preferably 10 ⁇ m or more. It is more preferably 25 ⁇ m or less.
  • the thickness of the multilayer polyimide film 10 can be measured using a laser holo gauge.
  • the thickness of the thermoplastic polyimide layer 12 (when two or more thermoplastic polyimide layers 12 are provided, the respective heats are provided.
  • the thickness of the plastic polyimide layer 12 is preferably 1 ⁇ m or more and 15 ⁇ m or less.
  • the thickness ratio of the non-thermoplastic polyimide layer 11 and the thermoplastic polyimide layer 12 is preferably 55/45 or more and 95/5 or less.
  • the thickness ratio is the ratio of the total thickness of each. Even if the number of layers of the thermoplastic polyimide layer 12 is increased, it is preferable that the total thickness of the thermoplastic polyimide layer 12 does not exceed the total thickness of the non-thermoplastic polyimide layer 11.
  • thermoplastic polyimide layers 12 are provided on both sides of the non-thermoplastic polyimide layer 11, and the same kind of heat is provided on both sides of the non-thermoplastic polyimide layer 11. It is more preferable that the thermoplastic polyimide layer 12 containing the thermoplastic polyimide is provided.
  • the thermoplastic polyimide layers 12 are provided on both sides of the non-thermoplastic polyimide layer 11, the thicknesses of the two thermoplastic polyimide layers 12 are the same in order to suppress the warp of the multilayer polyimide film 10. Is preferable.
  • the thickness of the other thermoplastic polyimide layer 12 is 40% or more and 100% based on the thickness of the thicker thermoplastic polyimide layer 12. If the range is less than the range, the warp of the multilayer polyimide film 10 can be suppressed.
  • the storage elastic modulus of the non-thermoplastic polyimide layer 11 at a temperature of 380 ° C. is preferably less than 0.350 GPa. It is more preferably less than 200 GPa. Further, from the viewpoint of improving the mechanical strength of the multilayer polyimide film 10 under high temperature, the storage elastic modulus is preferably 0.010 GPa or more, and more preferably 0.050 GPa or more. The storage elastic modulus can be adjusted, for example, by changing the content of BPDI residues. The method for measuring the storage elastic modulus is the same as or similar to that of the examples described later.
  • the temperature indicated by the variation point of the storage elastic modulus is the heat from the viewpoint of stress relaxation during laser processing and when the metal foil is bonded by the laminating method. From the viewpoint of stress relaxation, the range of 270 ° C. or higher and 340 ° C. or lower is preferable, and the range of 280 ° C. or higher and 330 ° C. or lower is more preferable.
  • the temperature indicated by the inflection point of the storage elastic modulus is within this range, the dimensional change at the temperature (for example, 250 ° C.) for evaluating the dimensional change after heating of the flexible metal-clad laminate can be suppressed.
  • the temperature indicated by the inflection point of the storage elastic modulus is low, the stress generated in the multilayer polyimide film 10 during cooling after laser processing becomes small.
  • the coefficient of linear expansion of the non-thermoplastic polyimide layer 11 is preferably 5.0 ppm / K or more and 19.0 ppm / K or less, more preferably 8.0 ppm / K or more and 15.0 ppm / K or less, and further preferably. Is 9.0 ppm / K or more and 12.0 ppm / K or less.
  • the coefficient of linear expansion of the multilayer polyimide film 10 is set to 14.0 ppm / K or more, which is close to that of copper foil, for example.
  • the linear expansion coefficient is, for example, the content of residues derived from a monomer having a rigid structure (more specifically, a PDA residue, etc.) and residues derived from a monomer having a bent structure (more specifically, an ODA residue). It can be adjusted by changing the content of (base, etc.).
  • the method for measuring the coefficient of linear expansion is the same as or similar to the embodiment described later.
  • the non-thermoplastic polyimide layer 11 preferably has a slope of the plastic deformation region in the stress-strain curve of 2.0 or more.
  • the plastic deformation region refers to the region of strain after the yield point in the stress-strain curve in the tensile test of the polyimide film.
  • the "difficult to plastically deform" property means that the stress is greatly increased in the plastic deformation region, or the stress required at the time of plastic deformation is large.
  • the inclination of the plastic deformation region is an index for the characteristic of "hard to be plastically deformed".
  • the slope of the plastic deformation region is, for example, the plastic deformation of the graph in which the vertical axis is "stress (unit: MPa)" and the horizontal axis is "strain (unit: mm)" for the result of measuring the tensile properties according to ASTM D882.
  • the slope of the s—s curve in the plastic deformation region can be calculated by the following formula. In the following equation, stress1 is a stress at 10% strain, stress2 is a fracture stress, strain1 is a 10% strain, and strain2 is a fracture strain.
  • the inclination of the plastic deformation region of the non-thermoplastic polyimide layer 11 is preferably 2.0 or more, more preferably 2.2 or more, and further preferably 2.5 or more.
  • the inclination of the plastic deformation region should be high, but in order to suppress the occurrence of springback and the like, the inclination of the plastic deformation region is preferably 4.5 or less, and 4.0 or less. Is more preferable.
  • the metal foil 13 is attached to at least one side of the multilayer polyimide film 10 (for example, in the case of FIG. 1, the surface 12a of the thermoplastic polyimide layer 12).
  • the metal-clad laminate 20 shown in FIG. 2 is obtained.
  • the method of adhering the metal foil 13 to the surface 12a of the thermoplastic polyimide layer 12 is not particularly limited, and various known methods can be adopted.
  • a thermal roll laminating device having a pair or more of metal rolls or a continuous processing method using a double belt press (DBP) can be adopted.
  • the specific configuration of the means for performing the thermal roll laminating is not particularly limited, but in order to improve the appearance of the obtained multi-layer polyimide film 10, between the pressure surface and the metal foil 13. It is preferable to place a protective material.
  • thermoplastic polyimide layer 12 When the thermoplastic polyimide layer 12 is provided on both sides of the non-thermoplastic polyimide layer 11, the double-sided metal-clad laminate (not shown) is formed by laminating the metal foil 13 on both sides of the multilayer polyimide film 10. can get.
  • the non-thermoplastic polyimide contained in the non-thermoplastic polyimide layer has a BPDI residue, an ODA residue, and a PDA residue as diamine residues.
  • the total content of BPDI residue, ODA residue and PDA residue is contained in all diamine residues constituting the non-thermoplastic polyimide.
  • the ratio is preferably 50 mol% or more, more preferably 70 mol% or more, further preferably 80 mol% or more, further preferably 90 mol% or more, and even more preferably 100 mol%. But it doesn't matter.
  • Examples of the diamine (monomer) for forming the BPDI residue include 4,4'-diamino-2,2'-dimethylbiphenyl (hereinafter, may be referred to as "m-TB"), 4,4. '-Diaminobiphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diamino-2,2'-dimethoxybiphenyl, 4,4'-diamino-3,3'-dimethoxybiphenyl, Examples thereof include 3,3', 5,5'-tetramethylbenzidine, 4,4'-bis (4-aminophenoxy) biphenyl and the like.
  • one or more diamines can be used as the diamine for forming the BPDI residue.
  • m-TB is preferable as the diamine (monomer) for forming the BPDI residue. That is, as the BPDI residue, the m-TB residue is preferable.
  • the content of ODA residues with respect to all diamine residues constituting the non-thermoplastic polyimide is set. It is preferably 40 mol% or more and 70 mol% or less, more preferably 45 mol% or more and 65 mol% or less, and further preferably 50 mol% or more and 65 mol% or less.
  • the content of PDA residues to all diamine residues constituting the non-thermoplastic polyimide is set. It is preferably 5 mol% or more and 50 mol% or less, more preferably 10 mol% or more and 40 mol% or less, and further preferably 15 mol% or more and 30 mol% or less.
  • the non-thermoplastic polyimide may have a diamine residue (another diamine residue) other than the BPDI residue, the ODA residue and the PDA residue as the diamine residue.
  • a diamine residue another diamine residue
  • an aromatic diamine having high heat resistance is preferable.
  • diamines for forming other diamine residues include 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, and 4,4'-diaminodiphenyl.
  • Non-thermoplastic polyimide has an acid dianhydride residue in addition to a diamine residue.
  • the acid dianhydride (monomer) for forming the acid dianhydride residue aromatic acid dianhydride is preferable from the viewpoint of improving heat resistance.
  • the acid dianhydride (monomer) for forming the acid dianhydride residue is an acid having a biphenyl skeleton. Dianhydride is preferred.
  • the acid dianhydride (monomer) for forming the acid dianhydride residue include pyromellitic acid dianhydride (hereinafter, may be referred to as "PMDA”), 3, 3', 4 , 4'-biphenyltetracarboxylic acid dianhydride (hereinafter sometimes referred to as "BPDA”), 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,2,5,6-naphthalene Tetracarboxylic acid dianhydride, 2,2', 3,3'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride (hereinafter referred to as "BTDA").
  • PMDA pyromellitic acid dianhydride
  • BPDA 4,4'-biphenyltetracarboxylic acid dianhydride
  • ODPA 4,4'-oxydiphthalic acid anhydride
  • 3,4 '-Oxydiphthalic anhydride 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, bis (3,4-dicarboxyphenyl) Phenyl) Propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3) -Dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) sulfon
  • the acid dianhydride residue is preferably one or more selected from the group consisting of BPDA residues and PMDA residues.
  • the BPDA residue having a biphenyl skeleton is preferable as the acid dianhydride residue.
  • the non-thermoplastic polyimide contains a BPDA residue, in order to further suppress the occurrence of cracks on the inner wall of the via during desmear treatment after laser processing while maintaining the linear expansion coefficient, all the non-thermoplastic polyimides are composed.
  • the content of the BPDA residue with respect to the acid dianhydride residue is preferably 10 mol% or more and 60 mol% or less, more preferably 20 mol% or more and 60 mol% or less, and 30 mol% or more and 60 mol. % Or less is more preferable.
  • the content of PMDA residues in the total acid dianhydride residues constituting the non-thermoplastic polyimide is 40 mol% or more and 80 mol% from the viewpoint of maintaining the linear expansion coefficient. It is preferably 40 mol% or more and 75 mol% or less, more preferably 40 mol% or more and 70 mol% or less.
  • the non-thermoplastic polyimide contains a BPDA residue and a PMDA residue
  • the BPDA residue and The total content of PMDA residues is preferably 60 mol% or more, more preferably 70 mol% or more, and more preferably 80 mol% with respect to the total acid dianhydride residues constituting the non-thermoplastic polyimide. It is more preferably% or more, and may be 100 mol%.
  • one or more non-thermoplastic polyimides are selected from the group consisting of BPDA residues and PMDA residues as acid dianhydride residues. And ODPA residues are preferred.
  • ODPA residues are preferred.
  • ODPA for the total acid dianhydride residue constituting the non-thermoplastic polyimide is used.
  • the residue content is preferably 5 mol% or more and 15 mol% or less.
  • the inner wall of the via is subjected to desmear treatment after laser processing while maintaining the coefficient of linear expansion.
  • the total content of BPDA residues, PMDA residues and ODPA residues is 80 mol% with respect to the total acid dianhydride residues constituting the non-thermoplastic polyimide. The above is preferable, 90 mol% or more is more preferable, and 100 mol% may be used.
  • the non-thermoplastic polyimide is represented by the following chemical formula (2). It is preferable to have a segment whose structural unit is a repeating unit.
  • a “segment” means a polymer chain formed from the same repeating unit which constitutes a block copolymer.
  • the "block copolymer” includes any aspect of a pure block copolymer, a random block copolymer, and a copolymer having a tapered block structure.
  • a segment having a structural unit represented by the chemical formula (2) as a repeating unit (hereinafter, may be referred to as a “specific segment”) can be formed by, for example, sequence polymerization described later.
  • the non-thermoplastic polyimide layer may contain components (additives) other than the non-thermoplastic polyimide.
  • a dye, a surfactant, a leveling agent, a plasticizer, a silicone, a filler, a sensitizer and the like can be used as the additive.
  • the content of the non-thermoplastic polyimide in the non-thermoplastic polyimide layer is, for example, 70% by weight or more, preferably 80% by weight or more, and more preferably 90% by weight or more, based on the total amount of the non-thermoplastic polyimide layer. It is more preferable, and it may be 100% by weight.
  • thermoplastic polyimide layer The thermoplastic polyimide contained in the thermoplastic polyimide layer has an acid dianhydride residue and a diamine residue.
  • the acid dianhydride (monomer) for forming the acid dianhydride residue in the thermoplastic polyimide is an acid dianhydride for forming the acid dianhydride residue in the non-thermoplastic polyimide described above (monomer).
  • the same compound as the monomer) can be mentioned.
  • the acid dianhydride residue contained in the thermoplastic polyimide and the acid dianhydride residue contained in the non-thermoplastic polyimide may be of the same type or different types from each other.
  • the diamine residue of the thermoplastic polyimide is preferably a diamine residue having a bent structure.
  • the content of the diamine residue having a bent structure is preferably 50 mol% or more, preferably 70 mol% or more, based on the total diamine residue constituting the thermoplastic polyimide. % Or more is more preferable, 80 mol% or more is further preferable, and 100 mol% may be used.
  • the diamine (monomer) for forming a diamine residue having a bent structure include 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, and 1,3.
  • BAPP 2,2-bis [4- (4-aminophenoxy) phenyl] propane
  • the thermoplastic polyimide layer may contain components (additives) other than the thermoplastic polyimide.
  • additive for example, a dye, a surfactant, a leveling agent, a plasticizer, a silicone, a filler, a sensitizer and the like can be used.
  • the content of the thermoplastic polyimide in the thermoplastic polyimide layer is, for example, 70% by weight or more, preferably 80% by weight or more, and more preferably 90% by weight or more, based on the total amount of the thermoplastic polyimide layer. Preferably, it may be 100% by weight.
  • the multilayer polyimide film according to the present embodiment preferably satisfies the following condition 1, and more preferably the following condition 2. It is more preferable to satisfy the following condition 3, still more preferably to satisfy the following condition 4, and particularly preferably to satisfy the following condition 5.
  • Condition 1 The non-thermoplastic polyimide has m-TB residue, ODA residue, PDA residue, BPDA residue and PMDA residue.
  • Condition 2 The content of the ODA residue with respect to all the diamine residues constituting the non-thermoplastic polyimide satisfying the above condition 1 is 40 mol% or more and 70 mol% or less.
  • Condition 3 The content of the PDA residue with respect to all the diamine residues constituting the non-thermoplastic polyimide satisfying the above condition 2 is 5 mol% or more and 50 mol% or less.
  • Condition 4 The non-thermoplastic polyimide satisfying the above condition 3 is a block copolymer having a specific segment.
  • Condition 5 The above condition 4 is satisfied, and the non-thermoplastic polyimide further has an ODPA residue.
  • the amount of each diamine and the amount of tetracarboxylic acid dianhydride (when using multiple types of tetracarboxylic acid dianhydride, when using multiple types of tetracarboxylic acid dianhydride, By adjusting the amount of each tetracarboxylic acid dianhydride), a desired polyamic acid (polymer of diamine and tetracarboxylic acid dianhydride) can be obtained.
  • the amount of substance ratio (molar ratio) of each residue in the polyimide formed from polyamic acid is consistent with, for example, the amount of substance ratio of each monomer (diamine and tetracarboxylic acid dianhydride) used for the synthesis of polyamic acid. ..
  • the temperature conditions for the reaction between the diamine and the tetracarboxylic dianhydride, that is, the synthetic reaction for the polyamic acid are not particularly limited, but are, for example, in the range of 20 ° C. or higher and 150 ° C. or lower.
  • the reaction time of the polyamic acid synthesis reaction is, for example, in the range of 10 minutes or more and 30 hours or less.
  • any method of adding a monomer may be used for producing the polyamic acid. The following methods can be mentioned as a typical method for producing a polyamic acid.
  • Examples of the method for producing a polyamic acid include a method of polymerizing by the following steps (Aa) and (Ab) (hereinafter, may be referred to as "A polymerization method").
  • a polymerization method A step of reacting an aromatic diamine with an aromatic acid dianhydride in an organic solvent in a state where the aromatic diamine is in excess to obtain a prepolymer having amino groups at both ends (A-a).
  • An aromatic dianhydride having a structure different from that used in the step (Aa) is additionally added, and an aromatic acid dianhydride having a structure different from that used in the step (Aa) is further added.
  • a method for producing the polyamic acid a method of polymerizing by the following steps (Ba) and the step (Bb) (hereinafter, may be referred to as “B polymerization method”) can also be mentioned.
  • a step of adding and polymerizing aromatic diamine so that the aromatic diamine and the aromatic acid dianhydride in all steps are substantially equimolar.
  • a polymerization method in which the order of addition of diamine and acid dianhydride is not set (a polymerization method in which monomers react arbitrarily with each other) is described as random polymerization in the present specification.
  • the polymer obtained by random polymerization is called a random copolymer.
  • sequence polymerization is preferable as a polymerization method for obtaining a polyimide effective for suppressing tearing of a film while maintaining the characteristics of a flexible metal-clad laminate.
  • the weight average molecular weight of the polyamic acid obtained by the above-mentioned polymerization method is preferably in the range of 10,000 or more and 1,000,000 or less, and more preferably in the range of 20,000 or more and 500,000 or less. It is more preferably in the range of 30,000 or more and 200,000 or less.
  • the weight average molecular weight used here means a polyethylene oxide equivalent value measured by gel permeation chromatography (GPC).
  • a method of obtaining the polyimide from a polyamic acid solution containing a polyamic acid and an organic solvent may be adopted.
  • the organic solvent that can be used in the polyamic acid solution include urea-based solvents such as tetramethylurea and N, N-dimethylethylurea; sulfoxide-based solvents such as dimethylsulfoxide; and diphenylsulfones and tetramethylsulfones.
  • N N-dimethylacetamide
  • N N-dimethylformamide
  • N N-diethylacetamide
  • N-methyl-2-pyrrolidone hexamethylphosphate
  • Amid solvents such as triamide; ester solvents such as ⁇ -butyrolactone; alkyl halide solvents such as chloroform and methylene chloride; aromatic hydrocarbon solvents such as benzene and toluene; phenol solvents such as phenol and cresol; cyclo Ketone-based solvents such as pentanone; ether-based solvents such as tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, dimethyl ether, diethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, and p-cresol methyl ether can be mentioned.
  • the reaction solution solution after the reaction
  • the organic solvent in the polyamic acid solution is the organic solvent used in the reaction in the above polymerization method.
  • a solid polyamic acid obtained by removing the solvent from the reaction solution may be dissolved in an organic solvent to prepare a polyamic acid solution.
  • Additives such as dyes, surfactants, leveling agents, plasticizers, silicones, and sensitizers may be added to the polyamic acid solution.
  • a filler may be added to the polyamic acid solution for the purpose of improving various properties of the film such as slidability, thermal conductivity, conductivity, corona resistance, and loop stiffness. Any filler may be used, and preferred examples thereof include fillers made of silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, mica and the like.
  • the concentration of the polyamic acid in the polyamic acid solution is not particularly limited, and is, for example, 5% by weight or more and 35% by weight or less, preferably 8% by weight or more and 30% by weight or less, based on the total amount of the polyamic acid solution.
  • concentration of polyamic acid is 5% by weight or more and 35% by weight or less, an appropriate molecular weight and solution viscosity can be obtained.
  • a step of peeling the gel film from the support after heating to obtain a self-supporting polyimide film (hereinafter, may be referred to as "gel film").
  • Step iv) The above gel film is heated.
  • the method of applying the doping solution on the support is not particularly limited, and a method using a conventionally known coating device such as a die coater, a comma coater (registered trademark), a reverse coater, and a knife coater is adopted. can.
  • the steps after step ii) are roughly divided into a thermal imidization method and a chemical imidization method.
  • the thermal imidization method is a method in which a polyamic acid solution is applied as a doping solution on a support and heated to proceed with imidization without using a dehydrating ring-closing agent or the like.
  • the chemical imidization method is a method of promoting imidization by using a polyamic acid solution to which at least one of a dehydration ring-closing agent and a catalyst is added as an imidization accelerator as a dope solution. Either method may be used, but the chemical imidization method is more productive.
  • an acid anhydride typified by acetic anhydride is preferably used.
  • tertiary amines such as aliphatic tertiary amines, aromatic tertiary amines, and heterocyclic tertiary amines are preferably used.
  • step iii As the support to which the dope solution is applied in step ii), a glass plate, aluminum foil, an endless stainless belt, a stainless drum, or the like is preferably used.
  • heating conditions are set according to the thickness of the finally obtained film and the production rate, and after at least one of partial imidization and drying is performed, the film is peeled off from the support to form a polyamic acid film (step iii). Gel film) is obtained.
  • step iv) water, the residual solvent, the imidization accelerator, etc. are removed from the gel film by fixing the end portion of the gel film and heat-treating it while avoiding shrinkage during curing, and the residue remains.
  • the polyamic acid is completely imidized to obtain a polyimide film containing a non-thermoplastic polyimide.
  • the heating conditions may be appropriately set according to the thickness of the finally obtained film and the production rate.
  • thermoplastic polyimide layer is, for example, a polyamic acid containing polyamic acid, which is a precursor of thermoplastic polyimide, on at least one side of a polyimide film (non-thermoplastic polyimide layer) obtained by using the above-mentioned non-thermoplastic polyimide solution.
  • a polyimide film non-thermoplastic polyimide layer obtained by using the above-mentioned non-thermoplastic polyimide solution.
  • thermoplastic polyamic acid solution After applying the solution (hereinafter, may be referred to as "thermoplastic polyamic acid solution"), it can be obtained by the same procedure as the above-mentioned method for forming a non-thermoplastic polyimide layer (polyimide film).
  • thermoplastic polyimide solution a solution containing thermoplastic polyimide (thermoplastic polyimide solution) is used to form a coating film made of the thermoplastic polyimide solution on at least one side of the non-thermoplastic polyimide layer, and this coating is performed.
  • the film may be dried to form a thermoplastic polyimide layer.
  • a coextruding die to form a laminate comprising a layer containing polyamic acid, which is a precursor of non-thermoplastic polyimide, and a layer containing polyamic acid, which is a precursor of thermoplastic polyimide.
  • the obtained laminate may be heated to form a non-thermoplastic polyimide layer and a thermoplastic polyimide layer at the same time.
  • a metal-clad laminate a laminate of a multilayer polyimide film and a metal foil
  • the above-mentioned coating step and heating step are repeated multiple times, or multiple coating films are formed by coextrusion or continuous coating (continuous casting) at one time.
  • the heating method is preferably used. It is also possible to perform various surface treatments such as corona treatment and plasma treatment on the outermost surface of the multi-layer polyimide film.
  • the metal foil one that has been subjected to surface treatment or the like according to the purpose and whose surface roughness or the like has been adjusted can be used. Further, a rust preventive layer, a heat resistant layer, an adhesive layer and the like may be formed on the surface of the metal foil.
  • the thickness of the metal foil is not particularly limited, and may be any thickness as long as it can exhibit sufficient functions depending on the intended use.
  • ⁇ Processing of metal-clad laminate> When a via is formed by laser processing using a metal-clad laminate as a material, the metal-clad laminate can be cut and a hole can be made by irradiating the portion to be processed with a laser.
  • Blind vias can be formed by penetrating a metal-clad laminate to form through holes, or by removing only the exposed polyimide layer after removing a part of the metal foil on the upper surface.
  • the metal foil on the upper surface is removed with a laser, and then the output of the laser is reduced to remove the polyimide layer, whereby the blind via can be stably formed.
  • a known type of laser can be adopted. Short wavelength lasers such as UV-YAG lasers and excimer lasers are preferred because they exhibit very high absorptance for both resins and metals.
  • a method of directly drilling a through hole is also widely used.
  • a desmear treatment method after laser processing a known method can be adopted, for example, a swelling step using an alkaline aqueous solution or a solution containing an organic solvent, an alkaline aqueous solution containing sodium permanganate, potassium permanganate, or the like.
  • a wet desmear treatment method including a roughening step and a neutralization step using the above can be mentioned.
  • the inner wall of the hole after desmear treatment is plated to make both sides of the metal-clad laminate conductive.
  • the plating method there is a method of adhering palladium to the inner wall surface of the hole and then forming an electroless copper plating layer on the inner wall surface using the palladium as a nucleus.
  • a plating layer having a desired thickness may be formed only by electrolytic copper plating, or a plating layer having a desired thickness may be formed by electrolytic copper plating after thinning the electrolytic copper plating layer. ..
  • the sample after laser processing was subjected to desmear treatment under the conditions shown in Table 2, and then the copper foil was removed by etching to obtain a sample for evaluation.
  • the manufacturer of the chemical solution used for the desmia treatment was Roam & Haas Electronic Materials Co., Ltd.
  • a washing step was carried out between the swelling step and the roughening step, between the roughening step and the neutralization step, and after the neutralization step.
  • the obtained evaluation sample was observed with a polarizing microscope under a cross Nicol at a magnification of 200 times to determine the presence or absence of cracks.
  • the state in which light leakage occurs around the holes is judged to be "cracking", and after observing 100 holes, the ratio of the cracked holes ( The crack occurrence rate) was calculated as a percentage.
  • 3 to 5 show an example of a polarizing microscope image used for actual discrimination.
  • FIG. 3 is an example of a hole where no crack has occurred because no light leakage has occurred around the hole.
  • 4 and 5 are examples of holes in which cracks are generated because light leakage occurs around the holes. For holes where the degree of light leakage was so weak that the presence or absence of cracks could not be determined, the cross section of the holes was observed with an electron microscope to determine the presence or absence of cracks.
  • the polyimide obtained from the polyamic acid in the obtained solution P1 was non-thermoplastic by the method shown below.
  • 32.5 g of an imidization accelerator composed of acetic anhydride / isoquinoline / DMF (weight ratio: 11.48 / 3.40 / 18.18) was added to 65 g of the solution P1 to prepare a doping solution.
  • the doping liquid was defoamed while stirring, and then the doping liquid was applied onto the aluminum foil using a comma coater to form a coating film.
  • the coating film was heated for 100 seconds under the condition of a heating temperature of 115 ° C. to obtain a self-supporting gel film.
  • the obtained gel film is peeled off from the aluminum foil, fixed to a metal fixing frame, heated for 15 seconds under the condition of a heating temperature of 250 ° C., and subsequently heated for 79 seconds under the condition of a heating temperature of 350 ° C. to dry. And imidization to obtain a polyimide film having a thickness of 12.5 ⁇ m.
  • the obtained polyimide film was fixed to a fixed frame made of metal and heated at a heating temperature of 450 ° C. for 2 minutes, the shape (film shape) of the polyimide film was maintained. Therefore, the polyimide obtained from the polyamic acid in the solution P1 was a non-thermoplastic polyimide.
  • the polyimide film obtained by the same method as the film forming method using the solution P1 is fixed to a metal fixing frame under the condition of a heating temperature of 450 ° C.
  • a heating temperature of 450 ° C When heated for 2 minutes, the shape of the polyimide film (film shape) was maintained. Therefore, the polyimides obtained from the polyamic acids in the solutions P2 to P12 were all non-thermoplastic polyimides.
  • a PMDA solution prepared in advance (solvent: DMF, PMDA dissolution amount: 0.87 g, PMDA concentration: 7.2% by weight) was added to the flask.
  • solvent DMF, PMDA dissolution amount: 0.87 g, PMDA concentration: 7.2% by weight
  • the addition of the PMDA solution and the stirring of the flask contents were stopped to obtain a solution P3 which is a non-thermoplastic polyamic acid solution.
  • a PMDA solution prepared in advance (solvent: DMF, PMDA dissolution amount: 0.94 g, PMDA concentration: 7.2% by weight) was added to the flask.
  • solvent DMF, PMDA dissolution amount: 0.94 g, PMDA concentration: 7.2% by weight
  • the addition of the PMDA solution and the stirring of the flask contents were stopped to obtain a solution P8 which is a non-thermoplastic polyamic acid solution.
  • a PMDA solution prepared in advance (solvent: DMF, PMDA dissolution amount: 0.89 g, PMDA concentration: 7.2% by weight) was added to the flask.
  • solvent DMF, PMDA dissolution amount: 0.89 g, PMDA concentration: 7.2% by weight
  • the addition of the PMDA solution and the stirring of the flask contents were stopped to obtain a solution P11 which is a non-thermoplastic polyamic acid solution.
  • a PMDA solution (solvent: DMF, PMDA dissolution amount: 0.81 g, PMDA concentration: 7.2% by weight) prepared in advance was added to the flask.
  • PMDA solution solvent: DMF, PMDA dissolution amount: 0.81 g, PMDA concentration: 7.2% by weight
  • the addition of the PMDA solution and the stirring of the flask contents were stopped to obtain a solution P12 which is a non-thermoplastic polyamic acid solution.
  • the polyimide obtained from the polyamic acid in the solution P13 was thermoplastic by the method shown below.
  • 30.0 g of an imidization accelerator composed of acetic anhydride / isoquinoline / DMF (weight ratio: 6.89 / 2.14 / 20.97) was added to 60 g of the solution P13 to prepare a doping solution.
  • the doping liquid was defoamed while stirring, and then the doping liquid was applied onto the aluminum foil using a comma coater to form a coating film.
  • the coating film was heated at a heating temperature of 120 ° C. for 3 minutes to obtain a self-supporting gel film.
  • the obtained gel film is peeled off from the aluminum foil, fixed to a metal fixing frame, heated at a heating temperature of 250 ° C. for 1 minute, and subsequently heated at a heating temperature of 300 ° C. for 200 seconds to dry. And imidization to obtain a polyimide film having a thickness of 20.0 ⁇ m.
  • the polyimide obtained from the polyamic acid in the solution P13 was a thermoplastic polyimide.
  • Example 1 A dope solution was prepared by adding 32.5 g of an imidization accelerator composed of acetic anhydride / isoquinoline / DMF (weight ratio: 11.48 / 3.40 / 18.18) to 65 g of the solution P1. Then, in an atmosphere of 0 ° C. or lower, the doping liquid was defoamed while stirring, and then the doping liquid was applied onto the aluminum foil using a comma coater to form a coating film. Then, the coating film was heated for 100 seconds under the condition of a heating temperature of 115 ° C. to obtain a self-supporting gel film.
  • an imidization accelerator composed of acetic anhydride / isoquinoline / DMF (weight ratio: 11.48 / 3.40 / 18.18)
  • the obtained gel film is peeled off from the aluminum foil, fixed to a metal fixing frame, heated for 15 seconds under the condition of a heating temperature of 250 ° C., and subsequently heated for 79 seconds under the condition of a heating temperature of 350 ° C. to dry. And imidization to obtain a polyimide film having a thickness of 12.5 ⁇ m.
  • Table 4 shows the physical characteristics of the obtained polyimide film (non-thermoplastic polyimide layer).
  • the "physical characteristics of the non-thermoplastic polyimide layer" in Table 4 are the physical characteristics measured using a polyimide film having a thickness of 12.5 ⁇ m.
  • the solution P13 is diluted with DMF until the solid content concentration becomes 8% by weight to prepare a dope solution, and then applied to both sides of the above-mentioned polyimide film (polyimide film obtained by using the solution P1) and applied. A film was formed. The coating amount at this time was adjusted so that the thickness of each formed thermoplastic polyimide layer (adhesive layer) was 3 ⁇ m.
  • the coating film was heated at a heating temperature of 120 ° C. for 2 minutes, and subsequently heated at a heating temperature of 350 ° C. for 15 seconds to dry and imidize, to obtain a multilayer polyimide film of Example 1.
  • Table 4 shows the results (crack generation rate) of the hole crack test of the obtained multi-layer polyimide film.
  • the copper-clad laminate produced during the hole crack test had no wrinkles on the surface and had a good appearance.
  • Example 2 to 7 and Comparative Examples 1 to 5 The multi-layer polyimide films of Examples 2 to 7 and Comparative Examples 1 to 5 were obtained by the same method as in Example 1 except that the non-thermoplastic polyamic acid solution shown in Table 4 was used instead of the solution P1. .. In each of Examples 2 to 7 and Comparative Examples 1 to 5, the amount of the non-thermoplastic polyamic acid solution used was 65 g. Table 4 shows the results (crack generation rate) of the hole crack test of the obtained multi-layer polyimide film. In Examples 2 to 4, Example 6, Example 7, and Comparative Examples 2 to 4, the copper-clad laminates produced during the hole crack test had no wrinkles on the surface and had a good appearance. was gotten. On the other hand, in Example 5, Comparative Example 1 and Comparative Example 5, there were wrinkles on a part of the surface of the copper-clad laminate prepared at the time of the hole crack test.
  • Table 3 shows the materials used for each of the solutions P1 to P13 and their ratios.
  • the substance amount ratio (molar ratio) of each residue in the polyimide obtained by using each of the solutions P1 to P13 is consistent with the substance amount ratio of each monomer (diamine and tetracarboxylic acid dianhydride) used. rice field.
  • Table 4 shows the types of non-thermoplastic polyamic acid solutions used, the physical properties of the non-thermoplastic polyimide layer, and the results of the whole crack test (crack generation rate) for each of Examples 1 to 7 and Comparative Examples 1 to 5. )showed that.
  • "-" means that the said component was not used.
  • the numerical value in the column of "acid dianhydride” is the content ratio (unit: mol%) of each acid dianhydride with respect to the total amount of acid dianhydride used.
  • the numerical value in the column of "diamine” is the content ratio (unit: mol%) of each diamine with respect to the total amount of diamines used.
  • the non-thermoplastic polyimide had an m-TB residue, which is a kind of BPDI residue, an ODA residue, and a PDA residue.
  • the content of m-TB residues was 20 mol% or more and 35 mol% or less with respect to all the diamine residues constituting the non-thermoplastic polyimide.
  • the crack occurrence rate was 50% or less.
  • the non-thermoplastic polyimides of Examples 1 to 4, 6 and 7 were block copolymers having specific segments, but the non-thermoplastic polyimides of Example 5 were random copolymers.
  • the multi-layer polyimide film according to the present invention can suppress the occurrence of cracks on the inner wall of the via during the desmear treatment after laser processing.
  • Multi-layer polyimide film 11 Non-thermoplastic polyimide layer 12: Thermoplastic polyimide layer

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Abstract

Film de polyimide multicouche (10) qui comprend une couche de polyimide non thermoplastique (11) et une couche de polyimide thermoplastique (12) qui est disposée sur au moins une surface de la couche de polyimide non thermoplastique (11). Un polyimide non thermoplastique qui est contenu dans la couche de polyimide non thermoplastique (11) a des résidus de dianhydride d'acide tétracarboxylique et des résidus de diamine. Les résidus de diamine comprennent un résidu de diamine ayant un squelette biphényle, un résidu de 4, 4'-diaminodiphényl éther et un résidu de p-phénylène diamine. La teneur du résidu de diamine qui a un squelette biphényle est de 20 % en moles à 35 % en moles par rapport à tous les résidus de diamine qui constituent le polyimide non thermoplastique.
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JP2019065180A (ja) * 2017-09-29 2019-04-25 日鉄ケミカル＆マテリアル株式会社 ポリイミドフィルム、金属張積層板及び回路基板

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