WO2016159104A1 - 多層ポリイミドフィルム、フレキシブル金属箔積層体、フレキシブル金属箔積層体の製造方法およびリジッドフレキシブル配線板の製造方法 - Google Patents

多層ポリイミドフィルム、フレキシブル金属箔積層体、フレキシブル金属箔積層体の製造方法およびリジッドフレキシブル配線板の製造方法 Download PDF

Info

Publication number
WO2016159104A1
WO2016159104A1 PCT/JP2016/060437 JP2016060437W WO2016159104A1 WO 2016159104 A1 WO2016159104 A1 WO 2016159104A1 JP 2016060437 W JP2016060437 W JP 2016060437W WO 2016159104 A1 WO2016159104 A1 WO 2016159104A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal foil
polyimide film
flexible
foil laminate
flexible metal
Prior art date
Application number
PCT/JP2016/060437
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
誠二 細貝
裕之 後
隼平 齋藤
小野　和宏
Original Assignee
株式会社カネカ
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 株式会社カネカ filed Critical 株式会社カネカ
Priority to JP2017510117A priority Critical patent/JP6580128B2/ja
Publication of WO2016159104A1 publication Critical patent/WO2016159104A1/ja

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • 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
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits

Definitions

  • the present invention relates to a multilayer polyimide film in which generation of cracks when immersed in a desmear liquid after hot pressing is suppressed, a flexible metal foil laminate having a multilayer polyimide resin layer and a metal foil, a method for producing a flexible metal foil laminate, and flexible
  • the present invention relates to a method for manufacturing a rigid flexible wiring board using a metal foil laminate.
  • a rigid flexible wiring board combining a rigid substrate and a flexible substrate as shown in FIG. 1 has come to be used. Since the semiconductor can be stably mounted on the rigid substrate and the flexible substrate can be bent, it is possible to achieve both high performance and downsizing of the rigid flexible wiring board.
  • the rigid flexible wiring board is manufactured by a process of laminating a rigid substrate and a flexible substrate (hereinafter also referred to as a flexible metal foil laminate) in a lump by hot pressing, and a laser processing step for forming an outer layer circuit.
  • a manufacturing method including a desmear process, and then a rigid flexible wiring board is manufactured through a copper plating process and an exterior circuit forming process.
  • a dummy board is used to eliminate the level difference as seen in FIG. 1, thereby equalizing the pressure applied to the rigid flexible wiring board in the manufacturing process. It was possible. However, in recent years, the use of dummy boards has been omitted in order to reduce manufacturing costs.
  • a step shown in FIG. 1 is obtained through a process of laminating and integrating by hot pressing, a laser processing process for forming an outer layer circuit, and a desmear process.
  • produces.
  • Japanese Patent Publication “JP 2002-144476 A Japanese Patent Publication “Japanese Patent Laid-Open No. 2010-114358 (published on May 20, 2010)” Japanese Patent Publication “Japanese Unexamined Patent Publication No. 2012-186377 (published September 27, 2012)”
  • Patent Documents 1 to 3 are not sufficient to withstand the rigid flexible printed wiring board manufacturing process that undergoes the process of laminating and integrating by hot pressing as described above and the process of desmear treatment. No polyimide material has been provided so far that cracks do not occur after both steps.
  • the present invention has been made in view of the above, and its purpose is to laminate and integrate a rigid substrate and a flexible substrate with a hot press and a desmear treatment step when manufacturing a rigid flexible wiring board.
  • Another object of the present invention is to provide a method for producing a flexible metal foil laminate and a method for producing a rigid flexible wiring board.
  • thermoplastic polyimide film on at least one surface of the non-thermoplastic polyimide resin layer.
  • the temperature at which the non-thermoplastic polyimide resin layer exhibits a maximum value of loss elastic modulus derived from ⁇ relaxation by dynamic viscoelasticity measurement is 155 ° C. to 185 ° C., and the maximum value is 0.1.
  • a flexible metal foil laminate comprising a metal foil on at least one surface of the multilayer polyimide film according to any one of ⁇ 1> to ⁇ 3>.
  • ⁇ 5> The method for producing a flexible metal foil laminate according to ⁇ 4>, comprising a step of casting a polyamic acid, which is a raw material of the multilayer polyimide film, onto the metal foil. Manufacturing method of foil laminated body.
  • the flexible metal foil laminate includes a multilayer polyimide film having at least one non-thermoplastic polyimide resin layer and a metal foil, and the multilayer Polyimide film derived from ⁇ relaxation by dynamic viscoelasticity measurement Manufacturing a rigid flexible wiring board characterized in that the temperature showing the maximum value of the loss elastic modulus is T-25 ° C to T + 5 ° C and the maximum value is 0.03 to 0.15 Method.
  • the flexible metal foil laminate obtained by the present invention can suppress the occurrence of cracks in the process of processing the flexible metal foil laminate into a rigid flexible wiring board.
  • a rigid flexible wiring board is a process of integrating a rigid substrate and a flexible substrate in a laminated state by collectively hot pressing (hereinafter also referred to as a heat pressing step), a laser processing step for forming an outer layer circuit, a desmear It is manufactured through a copper plating step and an exterior circuit forming step after a manufacturing step including a processing step.
  • a heat pressing step collectively hot pressing
  • a desmear It is manufactured through a copper plating step and an exterior circuit forming step after a manufacturing step including a processing step.
  • the boundary between the rigid substrate and the flexible substrate is as shown in FIG. Since there is a step, a strong thermal strain is applied to the flexible substrate.
  • the laser processing step for forming the outer layer circuit and the desmear treatment step are combined with the reduction in the strength of the resin film used for the flexible substrate by the alkaline solution used for the desmear treatment, and the above heat I found out that cracks would occur in the strained areas. That is, it has been found that the occurrence of cracks is caused by a desmear treatment step using an alkaline solution after the hot pressing step. Therefore, a material designed to withstand the thermal strain applied to the flexible metal foil laminate during the hot pressing process is insufficient to suppress cracks, and a material designed to withstand desmear treatment is also not cracked. It was found to be insufficient for suppression.
  • the present inventors think that it is sufficient to use a film that relieves stress in a hot pressing step in a process of manufacturing a rigid flexible wiring board as a film for use in a flexible substrate.
  • a film that relieves stress in the hot press process is considered that it can be achieved by a material having ⁇ dispersion near the temperature condition of the hot press process when dynamic viscoelasticity is measured. As a result of studying these materials, the present invention has been achieved.
  • the multilayer polyimide film according to the present invention is a multilayer polyimide film having at least one non-thermoplastic polyimide resin layer, and the multilayer polyimide film has a maximum value of loss elastic modulus derived from ⁇ relaxation by dynamic viscoelasticity measurement.
  • the temperature shown is from 155 ° C. to 185 ° C., and the maximum value of the loss elastic modulus derived from ⁇ relaxation is from 0.03 to 0.15.
  • the loss elastic modulus is a ratio (storage elastic modulus / loss elastic modulus) of storage elastic modulus and loss elastic modulus obtained by dynamic viscoelasticity measurement.
  • the dynamic viscoelasticity measurement of the resin sample is performed by defining the frequency of the applied stress and the temperature rising rate, and the value of tan ⁇ is plotted against the temperature.
  • tan ⁇ increases and shows a maximum value. Thereby, ⁇ relaxation can be confirmed.
  • dynamic viscoelasticity measurement is performed under the measurement conditions of a frequency of 5 Hz and a temperature increase rate of 3 ° C./min.
  • the multilayer polyimide film in the present invention is set so that the temperature showing the maximum value of tan ⁇ derived from ⁇ relaxation (hereinafter also referred to as the maximum temperature) is in the range of 155 ° C to 185 ° C.
  • the reason for setting in this way is that the maximum temperature of tan ⁇ derived from ⁇ relaxation is within this temperature range, assuming that the temperature often used in the hot press process when manufacturing a rigid flexible wiring board is around 180 ° C. This is because it was considered that the stress could be relaxed. If the maximum temperature deviates from the above temperature range, the temperature region where ⁇ relaxation occurs deviates from the temperature of the hot press process, and there is a possibility that sufficient thermal strain is not removed during the hot press process.
  • ⁇ relaxation is controlled to set the maximum temperature within the above temperature range.
  • the maximum temperature of tan ⁇ derived from ⁇ relaxation is in the range of 160 ° C. to 170 ° C. Within this range, the amount of stress relaxation is greater than the stress during the hot press process, enabling a hot press process at a higher pressure and lower temperature, and a process window in the hot press process. Is wide and preferable.
  • the maximum value is in the range of 0.03 to 0.15, preferably 0.04 to 0.12. When the maximum value of tan ⁇ derived from ⁇ relaxation is smaller than the above range, sufficient thermal strain may not be relaxed during hot pressing.
  • the temperature range showing the maximum value of tan ⁇ and the maximum value can be controlled by molecular design of polyimide as described later.
  • the dynamic viscoelasticity measurement of the multilayer polyimide film obtained by etching the metal foil is performed, and the maximum value of tan ⁇ derived from ⁇ relaxation and the temperature thereof are measured. Is possible.
  • the temperature range showing the maximum value of tan ⁇ of the non-thermoplastic polyimide resin layer and the maximum value thereof can be measured.
  • the multilayer polyimide film and the flexible metal foil laminate according to the present invention have a resin layer that expresses the above ⁇ relaxation, and thus are laminated and integrated in a hot pressing process when manufacturing a rigid flexible wiring board. At the same time, it is possible to remove thermal strain.
  • the temperature of the said hot press is not specifically limited, 170 degreeC or more and 190 degrees C or less (or 170 degreeC or more and less than 190 degreeC) may be sufficient, and 175 degreeC or more and 190 degrees C or less (or 175 degreeC or more and less than 190 degreeC) ), 180 ° C. or higher and 190 ° C. or lower (or 180 ° C. or higher and lower than 190 ° C.), 180 ° C. or higher and 185 ° C. or lower, or 180 ° C. Good.
  • the multilayer polyimide film and flexible metal foil laminate according to the present invention can be intended for use in the hot press described above.
  • the multilayer polyimide film according to the present invention has at least one non-thermoplastic polyimide resin layer.
  • the polyimide here is a polyamic acid produced by polymerizing aromatic diamine (hereinafter also referred to as diamine) and aromatic tetracarboxylic dianhydride (hereinafter also referred to as acid dianhydride) by a conventionally known method.
  • the polyamic acid is obtained by imidization.
  • the multilayer polyimide film has a temperature at which the maximum value of the loss elastic modulus derived from ⁇ relaxation as measured by dynamic viscoelasticity is 155 ° C. to 185 ° C., and the maximum value is 0.03 to 0.00.
  • the temperature at which the non-thermoplastic polyimide resin layer contained in the multilayer polyimide film exhibits the maximum value of the loss elastic modulus derived from ⁇ relaxation by dynamic viscoelasticity measurement is 155 ° C. to 185 ° C. It is preferable that the maximum value is 0.05 to 0.15 because the ⁇ dispersion of the entire multilayer polyimide film can be easily controlled to a target value.
  • the diamine used for manufacture of a non-thermoplastic polyimide resin layer Since the polyimide finally obtained needs to express beta relaxation, at least 1 type of diamine which is easy to express beta relaxation is used. It is preferable to use it. Since it depends on the structure of the acid dianhydride, a diamine that exhibits ⁇ relaxation cannot be uniquely determined. However, a biphenyl skeleton containing an alkyl group or a diamine having a phenyl skeleton, that is, an alkyl group-containing diaminobiphenyl component When a diamine containing is used, the resulting polyimide tends to exhibit ⁇ relaxation.
  • diamines include 4,4′-diamino-2,2′-dimethylbiphenyl, 4,4′-diamino-3,3′-dimethylbiphenyl, 4,4′-diamino-3,3′-. Hydroxybiphenyl, 1,4-diaminobenzene, 1,3-diaminobenzene, 4,4′-bis (4-aminophenoxy) biphenyl and the like, and 4,4′-diamino-2,2′-dimethylbiphenyl is Particularly preferred.
  • a diamine other than the above can be used as a part of the raw material as long as the finally obtained polyimide exhibits ⁇ relaxation.
  • diamines other than the above include 4,4′-diaminodiphenyl ether, 2,2-bis ⁇ 4- (4-aminophenoxy) phenyl ⁇ propane, 1,3-bis (4-aminophenoxy) benzene, 1 , 4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, and the like.
  • the acid dianhydride is not particularly limited, but it is preferable to use at least one acid dianhydride that easily exhibits ⁇ relaxation. Although it depends on the structure of the diamine, the acid dianhydride also tends to exhibit ⁇ relaxation when an acid dianhydride having a biphenyl skeleton or a phenyl skeleton is used. Specific examples include 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, and the like. As for the acid dianhydride, it is possible to use an acid dianhydride other than the above as a part of the raw material as long as the finally obtained polyimide exhibits ⁇ relaxation. Specific examples include 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, and the like.
  • the non-thermoplastic polyimide resin layer is preferably composed of an acid dianhydride and a diamine containing an alkyl group-containing diaminobiphenyl component.
  • the diamine containing an alkyl group-containing diaminobiphenyl component is preferably 4,4'-diamino-2,2'-dimethylbiphenyl.
  • the polyamic acid which is a polyimide precursor, is obtained by mixing and reacting diamine and acid dianhydride in an organic solvent so as to be substantially equimolar. Any organic solvent may be used as long as it dissolves polyamic acid, but amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, etc. N, N-dimethylformamide and N, N-dimethylacetamide can be used particularly preferably.
  • the solid content concentration of the polyamic acid is not particularly limited, and a polyamic acid having sufficient mechanical strength when obtained as a polyimide can be obtained as long as it is in the range of 5 wt% to 35 wt%.
  • the order of addition of the raw material diamine and acid dianhydride is not particularly limited, but it is possible to control the properties of the resulting polyimide by controlling not only the chemical structure of the raw material but also the order of addition. .
  • polyimide that exhibits ⁇ relaxation is essential, it is preferable to set the addition order so that a diamine that easily exhibits ⁇ relaxation and an acid dianhydride react preferentially.
  • a method of reacting diamine and acid dianhydride that are likely to exhibit ⁇ relaxation first, and then adding and reacting at least one of diamine and acid dianhydride for adjusting various properties include a method in which a diamine for adjusting properties and an acid dianhydride are reacted in advance, and then a diamine and an acid dianhydride that easily develop ⁇ relaxation are added and reacted.
  • the polyimide structure obtained by combining both has low durability against desmear liquid, so both are directly adjusted by adjusting the order of addition. It is preferred not to form a bonded structure.
  • a filler may be added for the purpose of improving various film properties such as slidability, thermal conductivity, conductivity, corona resistance, and loop stiffness.
  • Any filler may be used, but preferred examples include silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, and mica.
  • the polyamic acid is mixed with a thermosetting resin such as an epoxy resin or a phenoxy resin, or a thermoplastic resin such as polyether ketone or polyether ether ketone, as long as the properties of the resulting resin layer as a whole are not impaired. May be.
  • a method for adding these resins include a method in which the resin is added to the polyamic acid if the resin is soluble in a solvent. If the polyimide is also soluble in the solvent, the resin may be added to the polyimide solution. If the resin is insoluble in a solvent, there may be mentioned a method in which the polyamic acid is first imidized and then the polyimide and the resin are combined by melt kneading.
  • the multilayer polyimide film of the present invention preferably further has a thermoplastic polyimide film on at least one surface of the non-thermoplastic polyimide resin layer.
  • the aromatic diamine and aromatic tetracarboxylic dianhydride used for the thermoplastic polyimide film are the same as those used for the non-thermoplastic polyimide resin layer, but to make a thermoplastic polyimide film. It is preferable to react a flexible diamine with an acid dianhydride.
  • Examples of flexible diamines include 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 2,2-bis (4-aminophenoxyphenyl) ) Propane and the like.
  • acid dianhydrides that can be suitably combined with these diamines include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4, Examples thereof include 4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride and the like.
  • the following steps i) a step of reacting an aromatic diamine and an aromatic tetracarboxylic dianhydride in an organic solvent to obtain a polyamic acid solution; ii) casting a film-forming dope containing the polyamic acid solution on a support to form a resin layer; iii) a step of peeling the gel film from the support after heating the resin layer on the support; iv) further heating the gel film to imidize and dry the remaining amic acid, and It is preferable to contain. ii) Subsequent steps are roughly classified into a thermal imidization method and a chemical imidization method.
  • the thermal imidization method is a method in which a polyamic acid solution is used as a film-forming dope without using a dehydrating ring-closing agent or the like, and imidation is advanced only by heating and heating.
  • One chemical imidization method is a method in which imidization is promoted by using a polyamic acid solution to which at least one of a dehydrating cyclization agent and a catalyst is added as an imidization accelerator as a film-forming dope. Either the thermal imidization method or the chemical imidization method may be used, but the chemical imidization method is superior in productivity.
  • acid anhydrides typified by acetic anhydride
  • catalyst tertiary amines such as aliphatic tertiary amines, aromatic tertiary amines, and heterocyclic tertiary amines can be suitably used.
  • a glass plate, aluminum foil, endless stainless steel belt, stainless steel drum, or the like can be suitably used as the support for casting the film-forming dope. From the support after setting the heating conditions of the film-forming dope according to the thickness of the film finally obtained, the production rate, and performing at least one of imidization and drying partially on the film-forming dope It peels and a polyamic acid film (henceforth a gel film or a gel film) is obtained.
  • a plurality of resin layers may be formed simultaneously using a coextrusion die having a plurality of flow paths in the step ii).
  • a new resin layer may be formed thereon by coating or the like.
  • a multilayer polyimide film having a thermoplastic polyimide film on at least one surface of a non-thermoplastic polyimide resin layer is obtained, a non-thermoplastic polyimide precursor and a thermoplastic polyimide precursor are coextruded using a die. It can be obtained by casting on a support and carrying out the steps after iii).
  • thermoplastic polyimide film by coating, a precursor of a thermoplastic polyimide may be applied on a non-thermoplastic polyimide film and then imidized, or a thermoplastic polyimide solution may be applied to a non-thermoplastic polyimide film. You may apply
  • thermoplastic polyimide film may be obtained by casting a polyimide solution and cooling in place of casting the polyamic acid solution on the support in the above-described step.
  • the flexible metal foil laminate according to the present invention is composed of a multilayer polyimide film and a metal foil.
  • a means of forming a multilayer polyimide film on a metal foil a) Means (thermal laminating method) for obtaining a flexible metal foil laminate by bonding a metal foil to the multilayer polyimide film by heating and pressing after obtaining the multilayer polyimide film as described above, b) Casting an organic solvent solution containing polyamic acid on the metal foil, and heating to remove the solvent from the organic solvent solution and imidize to obtain a flexible metal foil laminate (casting method), c) On the metal foil, a means for obtaining a flexible metal foil laminate by casting a melt containing polyimide and cooling the melt (casting method), Is mentioned.
  • the flexible metal foil laminate is produced by a production method having a step of casting a polyamic acid, which is a raw material of the multilayer polyimide film, onto the metal foil.
  • the polyamic acid that is a raw material of the multilayer polyimide film cast on the metal foil may be (i) only a non-thermoplastic polyamic acid for forming a non-thermoplastic polyimide resin layer, or (ii) ) It may be only a thermoplastic polyamic acid for forming a thermoplastic polyimide film, or (iii) a non-thermoplastic polyamic acid and a thermoplastic polyimide film for forming a non-thermoplastic polyimide resin layer. Both of these thermoplastic polyamic acids may be used.
  • the means a) or b) If the polyimide is solvent-soluble, an organic solvent solution containing polyimide may be used instead of the organic solvent solution containing polyamic acid. Details of a) and b) will be described below.
  • the flexible metal foil laminate of the present invention is obtained by bonding a metal foil to the obtained multilayer polyimide film by heating and pressing.
  • the means and conditions for bonding the metal foil may be appropriately selected from conventionally known ones.
  • the means for casting the organic solvent solution containing polyamic acid on the metal foil is not particularly limited, and conventionally known techniques such as a die coater, comma coater (registered trademark), reverse coater, knife coater, etc. Means can be used. Conventionally known means can be used as the heating means for removing the solvent and imidizing, and examples thereof include a hot air furnace and a far infrared furnace.
  • the heating time can be shortened and the productivity can be improved by the chemical imidization method.
  • an acid is generated from an acid anhydride, which is a dehydrating ring-closing agent, in the imidization process, oxidation may proceed depending on the type of the metal foil.
  • the addition of the dehydrating ring-closing agent is preferably selected as appropriate according to the type of metal foil and heating conditions.
  • the immobilization is completed and the flexible metal foil laminate of the present invention is obtained at the same time.
  • the metal foil may be bonded to the surface of the resin layer opposite to the surface on which the metal foil layer is already provided by heating and pressing.
  • the total thickness of the multilayer polyimide film according to the present invention is preferably 7 ⁇ m to 60 ⁇ m. Even within that range, it is preferable that the thickness is small, since the bendability of the rigid flexible wiring board is improved. However, if the thickness is less than 7 ⁇ m, handling during processing may be difficult. When the thickness exceeds 60 ⁇ m, the bendability when a rigid flexible wiring board is obtained may be lowered.
  • metal foil which can be used in this invention
  • copper or copper alloy stainless steel
  • the foil which consists of the alloy, nickel or a nickel alloy (a 42 alloy is also included), aluminum, or an aluminum alloy can be mentioned.
  • copper foil such as rolled copper foil and electrolytic copper foil is frequently used, but it can also be preferably used in the present invention.
  • the antirust layer, the heat-resistant layer, or the contact bonding layer may be apply
  • it does not specifically limit about the thickness of the said metal foil According to the use, what is necessary is just the thickness which can exhibit a sufficient function.
  • the flexible metal foil laminate according to the present invention By using the flexible metal foil laminate according to the present invention as a flexible substrate and combining the flexible substrate and a rigid substrate such as a glass epoxy substrate, a rigid flexible wiring board is obtained.
  • the maximum temperature of tan ⁇ derived from ⁇ relaxation of the laminated polyimide film or the non-thermoplastic polyimide resin layer is controlled within the range of 155 ° C. to 185 ° C. The effect of mitigating thermal strain is exhibited within the temperature range of the process.
  • the temperature of the hot press (T ° C), which is a process of laminating and integrating the rigid substrate and the flexible substrate together by heating and pressing, contains polyimide. It is preferable that the tan ⁇ derived from ⁇ relaxation of the resin layer be equal to or higher than the temperature at which the maximum value is obtained.
  • T ° C the temperature of the hot press
  • the tan ⁇ derived from ⁇ relaxation of the resin layer be equal to or higher than the temperature at which the maximum value is obtained.
  • a rigid substrate and a flexible metal foil laminate are heated together under a temperature condition of T ° C. And pressurizing to form a rigid flexible substrate in which the rigid substrate and the flexible substrate are laminated and integrated, and applying laser processing to the rigid flexible substrate to provide an outer layer circuit on the rigid flexible substrate.
  • the flexible metal foil laminate in other words, the flexible substrate
  • the flexible substrate can include a multilayer polyimide film having at least one non-thermoplastic polyimide resin layer and a metal foil.
  • the temperature at which the multilayer polyimide film exhibits the maximum value of the loss elastic modulus derived from ⁇ relaxation by dynamic viscoelasticity measurement is T-25 ° C to T + 5 ° C (more preferably T-10 ° C to T ° C). And the maximum value may be 0.03 to 0.15 (more preferably 0.04 to 0.12).
  • the loss elastic modulus (tan-delta) in the dynamic viscoelasticity measurement of the polyimide in a synthesis example, an Example, and a comparative example and the crack resistance evaluation method at the time of desmear liquid immersion of a flexible metal foil laminated body are as follows.
  • the metal foil layer on one side of the cut laminate was etched to form a pattern having a wiring width of 250 ⁇ m and a wiring interval of 250 ⁇ m. All the metal foils on the non-patterned side were removed by etching.
  • a test piece having a length of 10 cm and a width of 1.5 cm was cut out from the laminate, with the direction parallel to the wiring as the longitudinal direction. As shown in FIG. 2, the test piece was sandwiched between laminated materials and subjected to hot pressing (first time) for 60 minutes under the conditions of 180 ° C. and 3.8 kgf / cm 2 .
  • a 10 cm ⁇ 12 cm glass epoxy substrate (FR4 substrate: thickness 0.4 mm) was used as a rigid substrate, and the central portion thereof was cut out so that an opening of 1 cm ⁇ 10 cm was formed. Then, double-sided tape was affixed to the remaining edge portion. The test piece is placed on the opening of the FR4 substrate so that the end of the test piece after the hot pressing is overlapped with the double-sided tape, and the rigid substrate and the flexible substrate are batched under the conditions of 180 ° C. and 30 kgf / cm 2. Heating and pressurization (hot pressing step (second time)) were performed for a minute.
  • hot pressing step second time
  • test piece was peeled off from the FR4 substrate, and the test piece was dessed in a swelling liquid maintained at 50 ° C. (Securigant P, manufactured by Atotech) for 90 seconds at 65 ° C.
  • the sample was sequentially immersed in a securigant P500 (P-Etch, manufactured by Atotech) for 300 seconds and in a neutralizing solution (secondary P500, manufactured by Atotech) maintained at 40 ° C. for 40 seconds. After immersion, the test piece was washed with water and then dried at 60 ° C. for 10 minutes.
  • an imidization accelerator consisting of acetic anhydride / isoquinoline / DMF (weight ratio 2.0 / 0.6 / 2.8) was added at a weight ratio of 50% with respect to the polyamic acid solution.
  • the mixture was stirred with a mixer, extruded from a T die, and cast onto a stainless steel endless belt. After heating this resin film at 130 ° C. ⁇ 100 seconds, the self-supporting gel film is peeled off from the endless belt and fixed to the tenter clip, and dried and imidized at 250 ° C. ⁇ 15 seconds, 350 ° C. ⁇ 87 seconds, A polyimide film having a thickness of 12.5 ⁇ m was obtained.
  • an imidization accelerator consisting of acetic anhydride / isoquinoline / DMF (weight ratio 2.0 / 0.6 / 2.7) was added at a weight ratio of 50% with respect to the polyamic acid solution.
  • the mixture was stirred with a mixer, extruded from a T die, and cast onto a stainless steel endless belt. After heating this resin film at 130 ° C. ⁇ 100 seconds, the self-supporting gel film is peeled off from the endless belt and fixed to the tenter clip, and dried and imidized at 250 ° C. ⁇ 15 seconds, 350 ° C. ⁇ 87 seconds, A polyimide film having a thickness of 12.5 ⁇ m was obtained.
  • an imidization accelerator composed of acetic anhydride / isoquinoline / DMF (weight ratio 2.0 / 0.6 / 3.0) was added at a weight ratio of 50% with respect to the polyamic acid solution.
  • the mixture was stirred with a mixer, extruded from a T die, and cast onto a stainless steel endless belt. After heating this resin film at 130 ° C. ⁇ 100 seconds, the self-supporting gel film is peeled off from the endless belt and fixed to the tenter clip, and dried and imidized at 250 ° C. ⁇ 15 seconds, 350 ° C. ⁇ 87 seconds, A polyimide film having a thickness of 12.5 ⁇ m was obtained.
  • an imidization accelerator consisting of acetic anhydride / isoquinoline / DMF (weight ratio 2.0 / 0.6 / 2.8) was added at a weight ratio of 50% with respect to the polyamic acid solution.
  • the mixture was stirred with a mixer, extruded from a T die, and cast onto a stainless steel endless belt. After heating this resin film at 130 ° C. ⁇ 100 seconds, the self-supporting gel film is peeled off from the endless belt and fixed to the tenter clip, and dried and imidized at 250 ° C. ⁇ 15 seconds, 350 ° C. ⁇ 87 seconds, A polyimide film having a thickness of 12.5 ⁇ m was obtained.
  • an imidization accelerator consisting of acetic anhydride / isoquinoline / DMF (weight ratio 2.0 / 0.6 / 3.8) was added at a weight ratio of 50% with respect to the polyamic acid solution.
  • the mixture was stirred with a mixer, extruded from a T die, and cast onto a stainless steel endless belt. After heating this resin film at 130 ° C. ⁇ 100 seconds, the self-supporting gel film is peeled off from the endless belt and fixed to the tenter clip, and dried and imidized at 250 ° C. ⁇ 15 seconds, 350 ° C. ⁇ 87 seconds, A polyimide film having a thickness of 12.5 ⁇ m was obtained.
  • an imidization accelerator consisting of acetic anhydride / isoquinoline / DMF (weight ratio 2.0 / 0.6 / 2.9) was added at a weight ratio of 50% with respect to the polyamic acid solution.
  • the mixture was stirred with a mixer, extruded from a T die, and cast onto a stainless steel endless belt. After heating this resin film at 130 ° C. ⁇ 100 seconds, the self-supporting gel film is peeled off from the endless belt and fixed to the tenter clip, and dried and imidized at 250 ° C. ⁇ 15 seconds, 350 ° C. ⁇ 87 seconds, A polyimide film having a thickness of 12.5 ⁇ m was obtained.
  • an imidization accelerator consisting of acetic anhydride / isoquinoline / DMF (weight ratio 2.0 / 0.6 / 2.9) was added at a weight ratio of 50% with respect to the polyamic acid solution.
  • the mixture was stirred with a mixer, extruded from a T die, and cast onto a stainless steel endless belt. After heating this resin film at 130 ° C. ⁇ 100 seconds, the self-supporting gel film is peeled off from the endless belt and fixed to the tenter clip, and dried and imidized at 250 ° C. ⁇ 15 seconds, 350 ° C. ⁇ 87 seconds, A polyimide film having a thickness of 12.5 ⁇ m was obtained.
  • an imidization accelerator consisting of acetic anhydride / isoquinoline / DMF (weight ratio 2.0 / 0.6 / 2.2) was added at a weight ratio of 50% with respect to the polyamic acid solution.
  • the mixture was stirred with a mixer, extruded from a T die, and cast onto a stainless steel endless belt. After heating this resin film at 130 ° C. ⁇ 100 seconds, the self-supporting gel film is peeled off from the endless belt and fixed to the tenter clip, and dried and imidized at 250 ° C. ⁇ 15 seconds, 350 ° C. ⁇ 87 seconds, A polyimide film having a thickness of 12.5 ⁇ m was obtained.
  • an imidization accelerator consisting of acetic anhydride / isoquinoline / DMF (weight ratio 2.0 / 0.6 / 2.8) was added at a weight ratio of 50% with respect to the polyamic acid solution.
  • the mixture was stirred with a mixer, extruded from a T die, and cast onto a stainless steel endless belt. After heating this resin film at 130 ° C. ⁇ 100 seconds, the self-supporting gel film is peeled off from the endless belt and fixed to the tenter clip, and dried and imidized at 250 ° C. ⁇ 15 seconds, 350 ° C. ⁇ 87 seconds, A polyimide film having a thickness of 12.5 ⁇ m was obtained.
  • Example 1 The polyamic acid solution obtained in Synthesis Example 11 was applied to both sides of the polyimide film obtained in Synthesis Example 1 so that the final thickness per side was 3.0 ⁇ m, and dried at 140 ° C. for 2 minutes. Subsequently, imidization was performed by heating at 350 ° C. for 1 minute to obtain a laminated polyimide film having a total thickness of 18.5 ⁇ m.
  • An electrolytic copper foil (3EC-M3S-HTE, made by Mitsui Metals) having a thickness of 12.5 ⁇ m is disposed on both sides of the obtained laminated polyimide film, and a protective film (Apical 125 NPI) is placed on the outside of both electrolytic copper foils.
  • a flexible metal foil laminate from the outside of the protective film, with a laminating temperature of 360 ° C., a laminating pressure of 265 N / cm (27 kgf / cm), and a laminating speed of 1.0 m / min. was made.
  • Example 2 The polyamic acid solution obtained in Synthesis Example 11 was coated on a 12.5 ⁇ m thick electrolytic copper foil (3EC-M3S-HTE, manufactured by Mitsui Metals) as a metal foil so that the final thickness after imidization was 3 ⁇ m. And dried at 120 ° C. for 2 minutes. Further, the polyamic acid solution obtained in Synthesis Example 1 was applied from above the dried polyamic acid solution using a bar coater so that the thickness after imidization was 12.5 ⁇ m, and dried at 130 ° C. for 5 minutes.
  • 3EC-M3S-HTE electrolytic copper foil
  • the polyamic acid solution obtained in Synthesis Example 11 was applied onto the dried polyamic acid solution using a bar coater so that the final thickness after imidization was 3 ⁇ m, and dried at 120 ° C. for 2 minutes. The temperature was raised to 350 ° C. over a period of time to complete imidization to obtain a single-sided flexible metal foil laminate.
  • An electrolytic copper foil having a thickness of 12.5 ⁇ m (3EC-M3S-HTE, manufactured by Mitsui Metals) is disposed on the surface of the single-sided flexible metal foil without the electrolytic copper foil, and a protective film (Apical 125 NPI; From the outside of the protective film, heat lamination is performed under conditions of a laminating temperature of 360 ° C., a laminating pressure of 265 N / cm (27 kgf / cm), and a laminating speed of 1.0 m / min. Was made.
  • Example 3 A flexible metal foil laminate was produced in the same manner as in Example 1 except that the polyimide film obtained in Synthesis Example 2 was used instead of the polyimide film obtained in Synthesis Example 1.
  • Example 4 A flexible metal foil laminate was produced in the same manner as in Example 2 except that the polyamic acid obtained in Synthesis Example 2 was used instead of the polyamic acid obtained in Synthesis Example 1.
  • Example 5 A flexible metal foil laminate was prepared in the same manner as in Example 1 except that the polyimide film obtained in Synthesis Example 3 was used instead of the polyimide film obtained in Synthesis Example 1.
  • Example 6 A flexible metal foil laminate was produced in the same manner as in Example 2 except that the polyamic acid obtained in Synthesis Example 3 was used instead of the polyamic acid obtained in Synthesis Example 1.
  • Example 7 A flexible metal foil laminate was prepared in the same manner as in Example 1 except that the polyimide film obtained in Synthesis Example 4 was used instead of the polyimide film obtained in Synthesis Example 1.
  • Example 8 A flexible metal foil laminate was produced in the same manner as in Example 2 except that the polyamic acid obtained in Synthesis Example 4 was used instead of the polyamic acid obtained in Synthesis Example 1.
  • Example 9 A flexible metal foil laminate was produced in the same manner as in Example 1 except that the polyimide film obtained in Synthesis Example 5 was used instead of the polyimide film obtained in Synthesis Example 1.
  • Example 10 A flexible metal foil laminate was produced in the same manner as in Example 2 except that the polyamic acid obtained in Synthesis Example 5 was used instead of the polyamic acid obtained in Synthesis Example 1.
  • Example 11 A flexible metal foil laminate was produced in the same manner as in Example 1 except that the polyimide film obtained in Synthesis Example 6 was used instead of the polyimide film obtained in Synthesis Example 1.
  • Example 12 A flexible metal foil laminate was produced in the same manner as in Example 2 except that the polyamic acid obtained in Synthesis Example 6 was used instead of the polyamic acid obtained in Synthesis Example 1.
  • a flexible metal foil laminate was produced by performing the same operation as in Example 1 except that a polyimide film having a thickness of 12.5 ⁇ m (Apical NPI, manufactured by Kaneka Corporation) was used. .
  • Table 1 shows the maximum temperature and maximum value of tan ⁇ derived from ⁇ relaxation of the non-thermoplastic polyimide resin layers and laminated polyimide films used in Examples, Comparative Examples and Reference Examples, and crack resistance results of flexible metal foil laminates. Show.
  • Examples 1 to 12 did not generate cracks.
  • the fact that the resin layer exhibits ⁇ relaxation indicates that thermal strain during hot pressing is relaxed.
  • Examples 3 to 10 had a higher evaluation of crack resistance than Examples 1, 2, 11, and 12.
  • the present invention can be used in the field of manufacturing flexible printed wiring boards.
  • Metal foil 1 Metal foil (inner layer circuit) 2. Glass epoxy board (FR4 board) 3. Adhesive 4. 4. Coverlay film Adhesive 6. 6. Multilayer polyimide film Nonwoven fabric 8. Metal plate 9. Craft 10. Vinyl chloride 11. Release film 12. Electrolytic copper foil 100. Rigid substrate 101. Flexible substrate 200. Laminate (7, 8, 9, 10, 11) 201. Flexible metal foil laminate

Landscapes

  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)
  • Structure Of Printed Boards (AREA)
PCT/JP2016/060437 2015-03-31 2016-03-30 多層ポリイミドフィルム、フレキシブル金属箔積層体、フレキシブル金属箔積層体の製造方法およびリジッドフレキシブル配線板の製造方法 WO2016159104A1 (ja)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2017510117A JP6580128B2 (ja) 2015-03-31 2016-03-30 リジッドフレキシブル配線板の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-074449 2015-03-31
JP2015074449 2015-03-31

Publications (1)

Publication Number Publication Date
WO2016159104A1 true WO2016159104A1 (ja) 2016-10-06

Family

ID=57006868

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/060437 WO2016159104A1 (ja) 2015-03-31 2016-03-30 多層ポリイミドフィルム、フレキシブル金属箔積層体、フレキシブル金属箔積層体の製造方法およびリジッドフレキシブル配線板の製造方法

Country Status (3)

Country Link
JP (2) JP6580128B2 (zh)
TW (1) TW201700302A (zh)
WO (1) WO2016159104A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190038381A (ko) 2017-09-29 2019-04-08 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 금속장 적층판 및 회로 기판
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

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113395843B (zh) * 2020-03-13 2022-11-15 宏启胜精密电子(秦皇岛)有限公司 具有断差的电路板及电路板的制造方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002144476A (ja) * 2000-08-28 2002-05-21 Ube Ind Ltd レ−ザ−加工性の良好なポリイミドフィルム、基板及び加工法
JP2003127275A (ja) * 2001-10-23 2003-05-08 Ube Ind Ltd 銅張積層基板
JP2004006735A (ja) * 2002-03-22 2004-01-08 Ube Ind Ltd 半導体パッケ−ジ内部絶縁用ポリイミドフィルムおよび積層基板
JP2005041049A (ja) * 2003-07-25 2005-02-17 Ube Ind Ltd 広幅銅張り積層基板
JP2005125721A (ja) * 2002-11-19 2005-05-19 Ube Ind Ltd 金属薄膜付きポリイミドフィルム
JP2010114358A (ja) * 2008-11-10 2010-05-20 Kaneka Corp デスミア処理する方法
JP2012186377A (ja) * 2011-03-07 2012-09-27 Ube Ind Ltd ポリイミド金属積層体の製造方法
WO2013157565A1 (ja) * 2012-04-19 2013-10-24 宇部興産株式会社 熱融着性ポリイミドフィルム、熱融着性ポリイミドフィルムの製造方法及び熱融着性ポリイミドフィルムを用いたポリイミド金属積層体

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4652020B2 (ja) * 2004-11-16 2011-03-16 新日鐵化学株式会社 銅張り積層板
JP2014041969A (ja) * 2012-08-23 2014-03-06 Sumitomo Electric Printed Circuit Inc プリント配線板の製造方法
JP6320031B2 (ja) * 2012-12-28 2018-05-09 新日鉄住金化学株式会社 フレキシブル銅張積層板
JP6056611B2 (ja) * 2013-03-29 2017-01-11 三菱マテリアル株式会社 交換式切削ヘッド
JP5976588B2 (ja) * 2013-03-29 2016-08-23 新日鉄住金化学株式会社 フレキシブル銅張積層板の製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002144476A (ja) * 2000-08-28 2002-05-21 Ube Ind Ltd レ−ザ−加工性の良好なポリイミドフィルム、基板及び加工法
JP2003127275A (ja) * 2001-10-23 2003-05-08 Ube Ind Ltd 銅張積層基板
JP2004006735A (ja) * 2002-03-22 2004-01-08 Ube Ind Ltd 半導体パッケ−ジ内部絶縁用ポリイミドフィルムおよび積層基板
JP2005125721A (ja) * 2002-11-19 2005-05-19 Ube Ind Ltd 金属薄膜付きポリイミドフィルム
JP2005041049A (ja) * 2003-07-25 2005-02-17 Ube Ind Ltd 広幅銅張り積層基板
JP2010114358A (ja) * 2008-11-10 2010-05-20 Kaneka Corp デスミア処理する方法
JP2012186377A (ja) * 2011-03-07 2012-09-27 Ube Ind Ltd ポリイミド金属積層体の製造方法
WO2013157565A1 (ja) * 2012-04-19 2013-10-24 宇部興産株式会社 熱融着性ポリイミドフィルム、熱融着性ポリイミドフィルムの製造方法及び熱融着性ポリイミドフィルムを用いたポリイミド金属積層体

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190038381A (ko) 2017-09-29 2019-04-08 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 금속장 적층판 및 회로 기판
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
JP7053208B2 (ja) 2017-09-29 2022-04-12 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

Also Published As

Publication number Publication date
JP2019204977A (ja) 2019-11-28
TW201700302A (zh) 2017-01-01
JP6793232B2 (ja) 2020-12-02
JP6580128B2 (ja) 2019-09-25
JPWO2016159104A1 (ja) 2017-12-21

Similar Documents

Publication Publication Date Title
KR100952796B1 (ko) 신규한 폴리이미드 필름 및 이를 이용하여 얻어지는 접착필름, 플렉시블 금속장 적층판
KR100958466B1 (ko) 신규한 폴리이미드 필름 및 그의 이용
JP5049594B2 (ja) 接着性の改良された新規なポリイミドフィルム
JP6788357B2 (ja) ポリイミドフィルム、多層ポリイミドフィルム、カバーレイ、及びフレキシブルプリント配線板
JP6793232B2 (ja) リジッドフレキシブル基板
JP2018145303A (ja) 多層ポリイミドフィルム
KR101096967B1 (ko) 접착 시트 및 동장 적층판
JP2006306973A (ja) 新規なポリイミドフィルム並びにそれを用いて得られる接着フィルム、フレキシブル金属張積層板
JP2006306972A (ja) 新規なポリイミドフィルム並びにそれを用いて得られる接着フィルム、フレキシブル金属張積層板
KR101244589B1 (ko) 접착성이 개량된 신규 폴리이미드 필름
JP2008188954A (ja) 片面金属張積層板用基材及び片面金属張積層板の製造方法
JP5468913B2 (ja) レジスト付き多層ポリイミドフィルム及びその製造方法
JP2019202514A (ja) 多層ポリイミドフィルム
JP6496812B2 (ja) ポリイミド積層フィルム、ポリイミド積層フィルムの製造方法、熱可塑性ポリイミドの製造方法、およびフレキシブル金属張積層体の製造方法
JP2011195771A (ja) 接着フィルムの製造方法ならびにフレキシブル金属張積層板
JP6522395B2 (ja) ポリイミドフィルム、フレキシブル金属張積層板、およびフレキシブルプリント配線板の製造方法
JP2005205806A (ja) 接着フィルムならびにそれから得られる寸法安定性を向上させたフレキシブル金属張積層板、ならびにその製造方法
JP2007050599A (ja) 寸法安定性に優れるフレキシブル金属張積層板およびその製造方法
WO2017170893A1 (ja) 長尺ポリイミド積層体およびその製造方法
JP2005193404A (ja) フレキシブル金属張積層板の製造方法
JP2006316232A (ja) 接着フィルムおよびその製造方法
JP5355993B2 (ja) 接着フィルム
JP2007296729A (ja) 寸法安定性に優れるフレキシブル金属張積層板およびその製造方法
JP2007296730A (ja) 寸法安定性に優れるフレキシブル金属張積層板およびその製造方法
JP2005194395A (ja) 接着フィルムならびにそれから得られる寸法安定性を向上させたフレキシブル金属張積層板

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16772985

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017510117

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16772985

Country of ref document: EP

Kind code of ref document: A1