WO2023203907A1 - 樹脂フィルム - Google Patents

樹脂フィルム Download PDF

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Publication number
WO2023203907A1
WO2023203907A1 PCT/JP2023/008825 JP2023008825W WO2023203907A1 WO 2023203907 A1 WO2023203907 A1 WO 2023203907A1 JP 2023008825 W JP2023008825 W JP 2023008825W WO 2023203907 A1 WO2023203907 A1 WO 2023203907A1
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Prior art keywords
resin
group
resin film
cof
norbornene
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PCT/JP2023/008825
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English (en)
French (fr)
Japanese (ja)
Inventor
隆 荒木
亮介 ▲高▼田
克行 養父
将士 上辺
正博 久保田
俊 坂井田
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Priority to CN202380015602.1A priority Critical patent/CN118488994A/zh
Priority to JP2024516126A priority patent/JP7635883B2/ja
Publication of WO2023203907A1 publication Critical patent/WO2023203907A1/ja
Priority to US18/651,238 priority patent/US20240287268A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/32—Modified amine-aldehyde condensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K2003/026—Phosphorus

Definitions

  • the present disclosure relates to a resin film.
  • the multilayer board mounted on such information communication equipment is manufactured from, for example, a copper clad laminate (CCL).
  • CCL includes a resin film. It is preferable that the resin composition constituting the resin film has a low dielectric constant and a low coefficient of thermal expansion in order to reduce warpage of the CCL. Furthermore, for Beyond 5G and 6G, which will enable even higher speed and larger capacity communications, resin compositions with even lower dielectric constants are required from the viewpoint of improving high frequency characteristics.
  • Patent Document 1 Japanese Patent Application Publication No. 2020-147677
  • Patent Document 3 Japanese Patent No. 4967116
  • Patent Document 4 Japanese Patent Application Publication No. 2007-231144
  • Patent Document 1 discloses a low dielectric resin composition that contains hollow particles consisting of a shell and a hollow part and a thermosetting resin, and in which 98% by mass or more of the entire shell of the hollow particles is formed of silica.
  • Patent Document 2 discloses a resin molded product containing an insulating resin and hollow particles having a shell layer containing silsesquioxane.
  • Patent Document 3 discloses a multilayer circuit board having an insulating layer composed of a porous insulating layer formed by dispersing particulate material in a synthetic resin and a non-porous insulating layer. Airgel is exemplified as a particulate material.
  • Patent Document 4 discloses a resin composition constituting a resin layer of a wiring board, which contains a low dielectric constant resin and zeolite.
  • Patent Document 5 Japanese Patent No. 2019-183005
  • Patent Document 6 International Publication No. 2008/081885
  • Patent Document 7 JP-A-2007-154169
  • Patent Document 8 JP 2003-147166
  • Patent Document 9 JP 7-099646
  • Patent Document 11 JP 2008-075079
  • Patent Document 12 Japanese Patent No. 6865687
  • the present disclosure has been made in view of the above problems, and aims to provide a resin film that can be suitably used for multilayer substrates.
  • the resin film based on the present disclosure consists of a resin composition that includes a resin component and a covalent organic structure in which a plurality of linker parts and a plurality of multidentate core parts are linked by covalent bonds.
  • the covalent organic structure has a network-like molecular skeleton that includes air with a low relative permittivity
  • the resin component when the relative permittivity of the resin component is relatively high, the resin component has a relatively high relative permittivity.
  • the dielectric constant of the composition can be lowered relative to the resin component.
  • the network-like molecular skeleton of the covalent organic structure is rigid because it has covalent bonds, and when the linear expansion coefficient of the resin component is relatively high, the linear expansion coefficient of the resin composition is It can be lowered compared to the ingredients.
  • the resin film based on the present disclosure can be suitably used for multilayer substrates.
  • FIG. 1 is a perspective view showing a resin film according to an embodiment of the present disclosure.
  • FIG. 1 is a perspective view schematically showing the structure of a two-dimensional COF among the covalent organic structures according to an embodiment of the present disclosure.
  • FIG. 1 is a perspective view showing a resin film according to an embodiment of the present disclosure.
  • the resin film 1 according to an embodiment of the present disclosure is made of a resin composition containing a resin component and a covalent organic structure, and is made of a multilayer resin substrate such as a flexible substrate or a rigid substrate (especially a high frequency circuit board). ) can be suitably used as a low dielectric layer included in
  • the thickness of the resin film 1 is, for example, 10 ⁇ m or more and 250 ⁇ m or less.
  • the resin composition according to the present embodiment preferably has a water absorption rate of 0.1% by mass or less when immersed in water at room temperature for 24 hours. Water has a relatively high dielectric constant. Therefore, if the above-mentioned water absorption rate is 0.1% by mass or less, the resin film made of the resin composition will suppress fluctuations in dielectric constant due to absorption of moisture, and can be more suitably used as a high-frequency circuit board member. can.
  • the melting point (Tm) of the resin composition according to this embodiment is preferably higher than 300°C. If the melting point (Tm) of the resin composition is over 300°C, the resin film made of the resin composition has good heat resistance and can be suitably used for high voltage circuit boards.
  • the melting point (Tm) of the resin composition is measured based on the storage modulus (E') using a dynamic viscoelasticity measurement device. Specifically, the melting point (Tm) of the resin composition is the temperature of the inflection point of the storage modulus (E') on the high temperature region side.
  • the resin composition according to the present embodiment has a dielectric constant of 3.0 when measured by applying a high frequency signal of 30 GHz at an ambient temperature of 25° C. using the cavity resonator method in accordance with JIS R 1641. It is preferably less than 2.8, more preferably less than 2.6. If the dielectric constant of the resin composition is less than 3.0, when the resin film is used for a high-frequency circuit board, transmission loss in the board can be more effectively suppressed.
  • the resin composition according to the present embodiment has a dielectric loss tangent of less than 0.002 when measured by applying a high frequency signal of 30 GHz at an ambient temperature of 25° C. using the cavity resonator method in accordance with JIS R 1641. It is preferable that it is, and it is more preferable that it is less than 0.001. If the dielectric loss tangent of the resin composition is less than 0.002, when the resin film is used for a high frequency circuit board, transmission loss in the board can be more effectively suppressed.
  • the resin composition according to the present embodiment preferably has a linear expansion coefficient in the in-plane direction when formed into a film of less than 59 ppm/°C, more preferably 40 ppm/°C or less, and 20 ppm/°C. It is more preferable that it is the following. If the linear expansion coefficient is less than 59 ppm/° C., when a circuit board is manufactured using a resin film made of the resin composition, warpage of the circuit board can be effectively suppressed.
  • the resin component according to this embodiment is a thermoplastic resin or a thermosetting resin.
  • the resin component is a thermoplastic resin
  • the resin film can be suitably used for the flexible substrate.
  • the resin component is appropriately selected from the viewpoint of electrical properties such as low dielectric constant or dielectric loss tangent, low water absorption, or heat resistance. Therefore, examples of thermoplastic resins include cyclic olefin resins, chain olefin resins, fluororesins, styrene resins, and liquid crystal polymers.
  • the resin component is a thermosetting resin
  • the resin film can be suitably used for the rigid substrate. Examples of the thermosetting resin include polyimide.
  • cyclic olefin polymer examples include addition polymers of cyclic olefin monomers and ring-opening polymers of cyclic olefin monomers.
  • addition polymers of cyclic olefin monomers include addition (co)polymers of norbornene type monomers obtained by polymerizing norbornene type monomers, and addition polymers of norbornene type monomers and polymers of ethylene, ⁇ -olefins, non-functional dienes, etc. Examples include addition copolymers with other monomers. Addition polymers of these cyclic olefin monomers can be obtained by known polymerization methods.
  • addition polymers of cyclic olefin resins include "TOPAS (registered trademark)” (manufactured by Ticona), which is an addition copolymer of norbornene and ethylene, and "APEL (registered trademark)” (manufactured by Mitsui Chemicals, Inc.). (manufactured by).
  • the addition polymer of a cyclic olefin monomer is preferably an addition polymer of a norbornene type monomer (hereinafter sometimes simply referred to as "polynorbornene") obtained by addition polymerizing a norbornene type monomer.
  • Polynorbornene has relatively low water absorption, high heat resistance, and low dielectric constant. Therefore, by using polynorbornene as a resin component, a resin film with low water absorption, high heat resistance, and low dielectric constant can be obtained.
  • Examples of addition polymers of norbornene type monomers include those containing a repeating structure represented by the following general formula (1).
  • X in formula (1) represents -CH 2 -, -CH 2 CH 2 -, or -O-, and R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom, a hydrocarbon group, a polar group having 1 to 12 carbon atoms, or an organic group containing the polar group.
  • n represents an integer from 0 to 2, and its repetition may be different.
  • R 1 , R 2 , R 3 and R 4 is a group containing a cyclic ether group having 1 to 12 carbon atoms, an organic group having a reactive double bond, or an alkoxysilyl group.
  • Examples of the above polar group having 1 to 12 carbon atoms include hydroxyl group, carboxyl group, ester group, acryloyl group, methacryloyl group, silyl group, epoxy group, ketone group, and ether group. Further, specific examples of the silyl group include alkoxysilyl groups such as trimethoxysilyl group and triethoxysilyl group.
  • the above organic group containing a polar group having 1 to 12 carbon atoms may be a linear or branched alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, a cycloaliphatic group, an aryl group, an ether group, or , and those bonded to the norbornene skeleton via a ketone group.
  • alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group;
  • alkenyl group Specific examples of alkynyl groups include vinyl group, allyl group, butynyl group, cyclohexenyl group, etc.; specific examples of alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, etc.; aralkyl group.
  • groups include benzyl group, phenethyl group, etc.; specific examples of cycloaliphatic groups include cyclopentyl group, cyclohexyl group, cyclooctyl group, etc.; specific examples of aryl groups include phenyl group, naphthyl group, anthracenyl group. etc.
  • organic group containing a polar group having 1 to 12 carbon atoms include an organic group containing a silyl group and an organic group containing an epoxy group.
  • organic groups containing silyl groups include diphenylmethylsilyl, triethoxysilylethyl, trimethoxysilylpropyl, and trimethylsilylmethyl ether groups;
  • organic groups containing epoxy groups include tylglycidyl ether group. , allylglycidyl-ether group, and the like.
  • the polynorbornene in the present disclosure is not limited to these.
  • a norbornene type monomer containing 2-norbornene and represented by the following general formula (2) is preferable.
  • X in formula (2) represents -CH 2 -, -CH 2 CH 2 -, or -O-, and R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom, a hydrocarbon group, a polar group having 1 to 12 carbon atoms, or an organic group containing the polar group.
  • n represents an integer from 0 to 2, and its repetition may be different.
  • norbornene type monomers having an alkyl group examples include 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-propyl-2-norbornene, 5-butyl-2-norbornene, and 5-pentyl-2-norbornene.
  • Examples include norbornene, 5-hexyl-2-norbornene, 5-heptyl-2-norbornene, 5-octyl-2-norbornene, 5-nonyl-2-norbornene, and 5-decyl-2-norbornene.
  • norbornene type monomers having an alkenyl group examples include 5-allyl-2-norbornene, 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-(2- propenyl)-2-norbornene, 5-(3-butenyl)-2-norbornene, 5-(1-methyl-2-propenyl)-2-norbornene, 5-(4-pentenyl)-2-norbornene, 5-( 1-Methyl-3-butenyl)-2-norbornene, 5-(5-hexenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-(2,3-dimethyl- 3-butenyl)-2-norbornene, 5-(2-ethyl-3-butenyl)-2-norbornene, 5-(3,4-dimethyl
  • Examples of the norbornene type monomer having an alkynyl group include 5-ethynyl-2-norbornene.
  • norbornene type monomers having a silyl group examples include 1,1,3,3,5,5-hexamethyl-1,5-dimethylbis((2-(5-norbornen-2-yl)ethyl)trisiloxane). It will be done.
  • norbornene type monomers having an alkoxysilyl group include dimethylbis((5-norbornen-2-yl)methoxy))silane, 5-trimethoxysilyl-2-norbornene, 5-triethoxysilyl-2-norbornene, 5- (2-trimethoxysilylethyl)-2-norbornene, 5-(2-triethoxysilylethyl)-2-norbornene, 5-(3-trimethoxypropyl)-2-norbornene, 5-(4-trimethoxybutyl) )-2-norbornene, 5-trimethylsilylmethyl ether-2-norbornene, and the like.
  • Examples of norbornene type monomers having an aryl group include 5-phenyl-2-norbornene, 5-naphthyl-2-norbornene, and 5-pentafluorophenyl-2-norbornene; examples of those having an aralkyl group include 5-benzyl-2-norbornene; Norbornene, 5-phenethyl-2-norbornene, 5-pentafluorophenylmethane-2-norbornene, 5-(2-pentafluorophenylethyl)-2-norbornene, 5-(3-pentafluorophenylpropyl)-2-norbornene Examples include.
  • Examples of the norbornene type monomer having a hydroxyl group, ether group, carboxyl group, ester group, acryloyl group or methacryloyl group include 5-norbornene-2-methanol and its alkyl ether, acetic acid 5-norbornene-2-methyl ester, and propionic acid.
  • 5-norbornene-2-methyl ester 5-norbornene-2-methyl butyrate, 5-norbornene-2-methyl valerate, 5-norbornene-2-methyl caproic acid, 5-norbornene-2-methyl caprylate Esters, capric acid 5-norbornene-2-methyl ester, lauric acid 5-norbornene-2-methyl ester, stearic acid 5-norbornene-2-methyl ester, oleic acid 5-norbornene-2-methyl ester, linolenic acid 5- norbornene-2-methyl ester, 5-norbornene-2-carboxylic acid, 5-norbornene-2-carboxylic acid methyl ester, 5-norbornene-2-carboxylic acid ethyl ester, 5-norbornene-2-carboxylic acid t-butyl ester , 5-norbornene-2-carboxylic acid i-butyl ester, 5-norbornene-2
  • Examples of the norbornene type monomer having an epoxy group include 5-[(2,3-epoxypropoxy)methyl]-2-norbornene.
  • Ring-opening polymers of cyclic olefin resins include ring-opening (co)polymers of norbornene-type monomers, hydrogenated ring-opening (co)polymers of norbornene-type monomers, norbornene-type monomers and ethylene, ⁇ -olefins, or non-ring-opening polymers. Examples include ring-opened copolymers with other monomers such as functional dienes, and hydrogenated ring-opened copolymers of norbornene-type monomers with ethylene, ⁇ -olefins, or norbornene-type monomers.
  • a hydrogenated ring-opening copolymer of a norbornene type monomer is preferred. Hydrogenated ring-opened copolymers of norbornene type monomers have relatively low water absorption and low dielectric constant. Therefore, by using a hydrogenated ring-opening copolymer of a norbornene type monomer as a resin component, a resin film with low water absorption and a low dielectric constant can be obtained.
  • ring-opening polymers of cyclic olefin resins include "ZEONOR (registered trademark)”, “ZEONEX (registered trademark)” (manufactured by Nippon Zeon Co., Ltd.), and “ARTON (registered trademark)”. ” (manufactured by JSR).
  • a chain olefin resin is an olefin resin that does not have a cyclic structure.
  • chain olefin resins include chain polyolefin resins such as polyethylene resins, polypropylene resins, and polymethylpentene resins. These chain polyolefin resins may have a linear structure or a branched structure.
  • polymethylpentene resin is preferred. Polymethylpentene resin has a relatively low dielectric constant. Therefore, by using polymethylpentene resin as the resin component, a resin film with a low dielectric constant can be obtained.
  • Commercially available polymethylpentene resins include "TPX (registered trademark)" (manufactured by Mitsui Chemicals, Inc.).
  • fluororesins examples include polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), fluorinated ethylene propylene (FEP), ethylenetetrafluoroethylene copolymer (ETFE), polyvinylidene fluorite (PVDF), and polyvinylidene fluorite (PVDF).
  • PTFE polytetrafluoroethylene
  • PFA perfluoroalkoxyalkane
  • FEP fluorinated ethylene propylene
  • ETFE ethylenetetrafluoroethylene copolymer
  • PVDF polyvinylidene fluorite
  • PVDF polyvinylidene fluorite
  • PVDF polyvinylidene fluorite
  • PVDF polyvinylidene fluorite
  • PCTFE chlorotrifluoroethylene
  • perfluoroalkoxyalkane is preferred as the fluororesin.
  • Perfluoroalkoxyalkanes have relatively low water absorption,
  • perfluoroalkoxyalkane as a resin component, a resin film having low water absorption, high heat resistance, and low dielectric constant can be obtained.
  • fluororesins include “Fluon (registered trademark) ETFE,” “Fluon (registered trademark) PTFE,” “Fluon (registered trademark) PFA,” and “Fluon+ (registered trademark) EA2000” (all manufactured by AGC Corporation). (manufactured by).
  • syndiotactic polystyrene As the styrene resin, syndiotactic polystyrene is preferred. Syndiotactic polystyrene has a relatively low dielectric constant. Therefore, by using syndiotactic polystyrene as a resin component, a resin film with a low dielectric constant can be obtained. Examples of commercially available syndiotactic polystyrene include "Oidys (registered trademark)" (manufactured by Kurabo Industries, Ltd.).
  • the liquid crystal polymer is not particularly limited, but examples include thermotropic liquid crystal polymers.
  • the thermotropic liquid crystal polymer is, for example, an aromatic polyester synthesized mainly from monomers such as aromatic diol, aromatic dicarboxylic acid, and aromatic hydroxycarboxylic acid, and exhibits liquid crystallinity when melted.
  • thermotropic liquid crystal polymers that do not have an amide bond
  • thermotropic liquid crystal polymers that do not have an amide bond include type 1 liquid crystal polymers and type 1.5 (or type 3) liquid crystal polymers.
  • the type 1 liquid crystal polymer is a copolymer of parahydroxybenzoic acid, terephthalic acid, and dihydroxybiphenyl (a copolymer of parahydroxybenzoic acid and ethylene terephthalate).
  • the 1.5 type liquid crystal polymer is a copolymer of parahydroxybenzoic acid and 2,6-hydroxynaphthoic acid, and has a melting point between the type 1 liquid crystal polymer and the type 2 liquid crystal polymer.
  • the liquid crystal polymer is preferably a 1.5 type liquid crystal polymer.
  • the 1.5-type liquid crystal polymer has relatively low water absorption, high heat resistance, and low coefficient of thermal expansion. Therefore, by using a 1.5-type liquid crystal polymer as the thermoplastic resin, a resin film can be obtained that has low water absorption, high heat resistance, and a low coefficient of thermal expansion.
  • the polyimide is not particularly limited as long as it is a resin having an imide bond in its repeating unit. More specifically, the polyimide is preferably an aromatic polyimide in which aromatic compounds are directly connected through imide bonds. Polyimide has relatively high heat resistance and a low coefficient of linear expansion. Therefore, by using a low polyimide as the thermosetting resin, a resin film with high heat resistance and a low coefficient of thermal expansion can be obtained. Polyimide can be obtained, for example, by heat-treating a polyimide precursor solution. Examples of commercially available polyimide precursor solutions include "Uimide (registered trademark)" (manufactured by Unitika) and "Yupia (registered trademark)” (manufactured by Ube Industries, Ltd.).
  • the resin component according to the present embodiment preferably has a water absorption rate of 0.1% by mass or less when immersed in water at room temperature for 24 hours. Water has a relatively high dielectric constant. Therefore, if the water absorption rate of the resin component is 0.1% by mass or less, the water absorption rate of the resin composition according to this embodiment will also be low. Furthermore, the resin film made of the resin composition is suppressed from changing its dielectric constant due to moisture absorption, and can be more suitably used as a high-frequency circuit board member.
  • the melting point (Tm) of the resin component according to this embodiment is preferably higher than 300°C. If the melting point (Tm) of the resin component is higher than 300° C., the melting point (Tm) of the resin composition containing this resin component will also be relatively high. Furthermore, since the resin film made of the resin composition has good heat resistance, it can be suitably used for high voltage circuit boards.
  • the melting point (Tm) of the resin component is measured based on the storage modulus (E') using a dynamic viscoelasticity measurement device. Specifically, the melting point (Tm) of the resin component is the temperature of the inflection point of the storage modulus (E') on the high temperature region side.
  • the resin component according to this embodiment has a relative dielectric constant of less than 3.0 when measured by applying a high frequency signal of 30 GHz at an ambient temperature of 25° C. using the cavity resonator method in accordance with JIS R 1641. It is preferably less than 2.8, more preferably less than 2.6. If the dielectric constant of the resin component is less than 3.0, the dielectric constant of the resin composition will also be low. Furthermore, when the resin film according to this embodiment is used in a high-frequency circuit board, transmission loss in the board can be suppressed more effectively.
  • the resin component according to this embodiment has a dielectric loss tangent of less than 0.002 when measured by applying a high frequency signal of 30 GHz at an ambient temperature of 25° C. using the cavity resonator method in accordance with JIS R 1641. It is preferably present, and more preferably less than 0.001.
  • a resin composition containing a resin component having a dielectric loss tangent of less than 0.002 has a relatively low dielectric loss tangent. Therefore, when a film made of the resin composition is used for a high-frequency circuit board, transmission loss in the board can be suppressed more effectively.
  • the resin component according to this embodiment preferably has a linear expansion coefficient in the in-plane direction when formed into a film of less than 59 ppm/°C, more preferably less than 40 ppm/°C, and more preferably less than 20 ppm/°C. It is more preferable that If the linear expansion coefficient is less than 59 ppm/°C, the linear expansion coefficient of the resin composition containing the resin component will also be relatively low. Therefore, when a circuit board is manufactured using a film made of the resin composition, warping of the circuit board can be effectively suppressed.
  • Covalent organic frameworks (COF) contained in the resin composition according to the present embodiment are porous crystalline particles in which organic structures are covalently bonded to each other to form a periodic structure, COF is in powder form.
  • the COF according to this embodiment is a structure in which a plurality of linker parts and a plurality of multidentate core parts are linked by covalent bonds.
  • COF has a network-like molecular skeleton in which many pores are formed.
  • the multidentate core part is an organic structural part located at a branch point of the mesh-like molecular skeleton of COF
  • the linker part is an organic structural part that connects two multidentate core parts located on both sides of the linker part. be.
  • the type of covalent bond in COF may be a single bond, double bond, or triple bond, but from the viewpoint of ease of synthesis of COF and improvement of rigidity of COF, it is preferable to use double bond. is preferred. If the covalent bond of the COF is a double bond, the COF will have a more rigid structure, and the linear expansion coefficient of the resin composition containing the COF as a filler will decrease. Moreover, the covalent bond of COF is more preferably a carbon-nitrogen double bond (imine bond) in which a carbon atom (preferably a CH group) and a nitrogen atom are bonded to each other.
  • the linker part When the double bond between the linker part and the multidentate core part of COF is a carbon-nitrogen double bond (imine bond), the linker part has a carbon atom (preferably a CH group) constituting the imine bond, and also has a multidentate core part.
  • the core portion has a nitrogen atom forming an imine bond.
  • the linker portion has a nitrogen atom forming an imine bond
  • the polydentate core portion has a carbon atom (preferably a CH group) forming an imine bond.
  • the linker part has a structure in which two atoms (i.e., nitrogen atoms or carbon atoms) constituting an imine bond are each bonded to an aromatic compound, a heterocyclic compound, or a fused heterocyclic compound. have.
  • the aromatic compound bonded to the atoms constituting the imine bond in the linker part is one or more benzene rings, one or more fused polycyclic aromatic hydrocarbons, one or more heterocyclic aromatic compounds, or one or more fused
  • it contains a heterocyclic aromatic compound.
  • Examples of the linker portion include structures represented by the following chemical formulas (3) to (6).
  • n and m are each independently an integer of 0 or more and 10 or less, and R 1 to R 8 are each independently hydrogen, halogen, hydroxy group, alkyl group, alkoxy group, or aryl group. , a phosphine group, a phosphine oxide group, or an aromatic heterocyclic group, and X is a CH group or nitrogen.
  • n is an integer of 1 to 10
  • R 1 to R 4 each independently represent hydrogen, halogen, hydroxy group, alkyl group, alkoxy group, aryl group, phosphine group, phosphine oxide group or an aromatic heterocyclic group
  • X is a CH group or nitrogen.
  • R 1 to R 6 are each independently hydrogen, halogen, hydroxy group, alkyl group, alkoxy group, aryl group, phosphine group, phosphine oxide group, or aromatic heterocyclic group. and X is a CH group or nitrogen.
  • R 1 to R 6 are each independently hydrogen, halogen, hydroxy group, alkyl group, alkoxy group, aryl group, phosphine group, phosphine oxide group, or aromatic heterocyclic group. and X is a CH group or nitrogen.
  • the alkyl group may be linear or branched, or may be a cycloalkyl group.
  • the number of carbon atoms in the alkyl group is approximately 1 or more and 20 or less.
  • the alkoxy group may be linear or branched, or may be a cycloalkyloxy group.
  • the number of carbon atoms in the alkoxy group is approximately 1 or more and 20 or less.
  • An aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon.
  • Aryl groups include those having fused rings, independent benzene rings, or two or more fused rings bonded directly or via a group such as vinylene.
  • the polydentate core part has three or more atoms (i.e., nitrogen atoms or carbon atoms) constituting the imine bond, and is an aromatic compound, a heterocyclic compound, or a fused heterocyclic compound. It has a bonded structure.
  • the aromatic compound bonded to the atoms constituting the imine bond in the multidentate core is one or more benzene rings, one or more fused polycyclic aromatic hydrocarbons, one or more heterocyclic aromatic compounds, or one or more It is preferable to have a fused heterocyclic aromatic compound.
  • Examples of the multidentate core portion include structures represented by the following chemical formulas (7) to (9).
  • R 1 to R 3 are each independently hydrogen, halogen, hydroxy group, alkyl group, alkoxy group, aryl group, phosphine group, phosphine oxide group, or aromatic heterocyclic group. and X is a CH group or nitrogen.
  • R 1 to R 15 are each independently hydrogen, halogen, hydroxy group, alkyl group, alkoxy group, aryl group, phosphine group, phosphine oxide group, or aromatic heterocyclic group. and X is a CH group or nitrogen.
  • R 1 to R 16 are each independently hydrogen, halogen, hydroxy group, alkyl group, alkoxy group, aryl group, phosphine group, phosphine oxide group, or aromatic heterocyclic group. and X is a CH group or nitrogen.
  • the alkyl group may be linear or branched, or may be a cycloalkyl group.
  • the number of carbon atoms in the alkyl group is approximately 1 or more and 20 or less.
  • the alkoxy group may be linear or branched, or may be a cycloalkyloxy group.
  • the number of carbon atoms in the alkoxy group is approximately 1 or more and 20 or less.
  • An aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon.
  • Aryl groups include those having fused rings, independent benzene rings, or two or more fused rings bonded directly or via a group such as vinylene.
  • the linker part and/or the polydentate core part contain a phosphorus element, for example, a phosphine group or a phosphine oxide group.
  • a phosphorus element for example, a phosphine group or a phosphine oxide group.
  • the linker portion and/or the translocated core portion containing the phosphorus element flame retardancy can be imparted to the resin composition or the flame retardance of the resin composition can be improved.
  • the linker portion and/or the polylocated core portion have an alkyl group from the viewpoint of improving the hydrophobicity of the resin composition.
  • both ends of the linker part are carbon atoms
  • the multidentate core part has a nitrogen atom, so that the covalent bond of COF is between the carbon atom of the linker part and the nitrogen atom of the multidentate core part.
  • the atoms are carbon-nitrogen double bonds bonded to each other.
  • the resin composition obtained by adding such COF to the resin component has a rigid carbon-nitrogen double bond between the carbon atom in the linker part and the nitrogen atom in the multidentate core part, so that the dielectric loss tangent increases. is suppressed.
  • the linker part is bonded to the nitrogen atom of the polydentate core part. It has two carbon atoms bonded to it, and the polydentate core portion has three or more nitrogen atoms bonded to the carbon atoms of the linker portion.
  • the COF can easily form a so-called two-dimensional COF skeleton having a planarly expanding network structure.
  • the multidentate core portion has four nitrogen atoms bonded to the carbon atoms of the linker portion, a so-called three-dimensional COF skeleton having a three-dimensionally expanding network structure can be easily formed.
  • FIG. 2 is a perspective view schematically showing the structure of a two-dimensional COF among the covalent organic structures according to an embodiment of the present disclosure.
  • the covalent organic framework (COF) 10 is a structure in which a plurality of linker parts 11 and a plurality of multidentate core parts 12 are connected, and has a mesh-like skeleton.
  • COF 10 an example of a two-dimensional COF is shown as the COF 10, so this mesh-like skeleton is spread out in a plane.
  • COF10 has crystallinity, and as shown in FIG.
  • a plurality of mesh skeletons that spread in a plane are lined up along a direction that intersects the plane direction in which the mesh skeletons spread.
  • a plurality of holes formed by the network structures are located side by side along the direction in which the network structures are lined up. Therefore, a relatively large void is formed inside the two-dimensional COF 10 by lining up the plurality of holes.
  • the two-dimensional COF 10 can hold a relatively large amount of air in the void, and therefore has a low dielectric constant. Therefore, when the two-dimensional COF 10 is added to a resin component having a relatively high dielectric constant, a resin composition having a low dielectric constant relative to the resin component can be obtained.
  • COF examples include structures shown in the following chemical formulas (10) to (12), but COF is not limited to these.
  • the linker part has two nitrogen atoms located at both ends thereof, and the polydentate core part bonds with the nitrogen atoms located at both ends of the linker part. It has three carbon atoms (specifically CH groups). Therefore, the COF represented by the above formula (10) has a so-called two-dimensional COF structure having a network structure that spreads in a plane.
  • the linker part has two carbon atoms (specifically CH groups) located at both ends thereof, and the polydentate core part has two carbon atoms located at both ends of the linker part. It has three nitrogen atoms bonded to carbon atoms (specifically, CH groups). Therefore, the COF represented by the above formula (10) has a so-called two-dimensional COF structure having a network structure that spreads in a plane.
  • the linker part has two carbon atoms (specifically CH groups) located at both ends thereof, and the polydentate core part has two carbon atoms located at both ends of the linker part. It has four nitrogen atoms bonded to carbon atoms (specifically, CH groups). Therefore, the COF represented by the above formula (12) has a so-called three-dimensional COF structure having a three-dimensionally expanding network structure.
  • the content of the covalent organic structure is preferably 10% by volume or more, preferably 20% by volume or more, and more preferably 30% by volume or more based on the resin composition. If the content of the covalent organic structure is 10% by volume or more based on the resin composition, the linear expansion coefficient of the resin composition can be more effectively reduced, and if the content is 30% by volume or more, the content of the resin component can be reduced. Even when flame retardancy is relatively low, flame retardancy can be imparted to the resin composition. Further, the upper limit of the content of the covalent organic structure is not particularly limited, but from the viewpoint of suppressing the rigidity of the resin film from becoming excessively high, it is preferably 80% by volume or less, and 70% by volume or less. More preferably, it is 60% by volume or less.
  • the method for producing COF is not particularly limited, but when the covalent bond of COF is a carbon-nitrogen double bond (imine bond), a compound having multiple aldehyde groups and a compound having multiple amino groups are subjected to a dehydration condensation reaction.
  • COF can be obtained by doing this. That is, a linker compound has aldehyde groups at both ends and forms the linker part of COF by dehydration condensation reaction, and a linker compound has three or more amino groups and forms the multidentate core part of COF by dehydration condensation reaction.
  • a COF having an imine bond can be obtained by subjecting the locus core compound to a dehydration condensation reaction.
  • a COF having imine bonds can be obtained by decondensing a linker compound having amino groups at both ends and a multidentate core compound having three or more aldehyde groups.
  • a COF represented by the structure of the above formula (12) can be obtained by subjecting terephthalaldehyde as a linker compound and tetrakis(4-aminophenyl)methane as a polydentate core compound to a dehydration condensation reaction. Note that the method for manufacturing COFs represented by the structures of formulas (10) to (12) above is not limited to the above method.
  • the resin composition according to the present embodiment may contain other additives in addition to COF for the purpose of improving physical properties such as water absorption, heat resistance, and electrical properties.
  • the resin composition may contain an inorganic filler and an organic filler other than COF.
  • the inorganic filler and organic filler include hollow silica, hollow glass, zeolite, aerogel, and silsesquioxane.
  • the resin composition according to this embodiment may contain only COF as a filler.
  • the method for producing the resin film is not particularly limited. Prepare a resin solution by adding COF to a precursor solution of the resin component, apply the resin solution to a carrier film or directly apply it to other layers of a multilayer substrate, and heat the applied resin solution.
  • a resin film may be obtained by drying. COF is added to the heated and melted resin component, and this is stirred to obtain a molten resin composition, and then this resin composition is molded by injection molding or press molding to form a resin film. You may get it.
  • a resin film may be obtained by preparing a resin composition in which COF is added to the resin component in advance, heating the resin composition to melt it, and then molding it by injection molding or press molding. good.
  • ⁇ COF(a)> In ultrapure water, 2,6-diaminoanthraquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) (1 mol/L) as a linker compound and 2,4,6-triformylphloroglucinol (670 mmol/L) as a polydentate core compound were added. The mixture was stirred overnight at room temperature in the presence of p-toluenesulfonic acid monohydrate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) (5 mol/L) as an acid catalyst.
  • p-toluenesulfonic acid monohydrate manufactured by Tokyo Kasei Kogyo Co., Ltd.
  • ⁇ COF(b)> In a mixed solution in which 1,4-dioxane and mesitylene were mixed at a volume ratio of 4:1, terephthalaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) (37.5 mmol/L) was used as a linker compound and as a polydentate core compound. 1,3,5-tris(4-aminophenyl)benzene (manufactured by Tokyo Chemical Industry Co., Ltd.) (25 mmol/L) and Sc(OTf) 3 (manufactured by Tokyo Chemical Industry Co., Ltd.) (1.5 mmol/L) as a Lewis acid catalyst. ) at room temperature for 1 hour.
  • ⁇ COF(c)> In a mixed solution in which 1,4-dioxane and mesitylene were mixed at a volume ratio of 4:1, terephthalaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) (37.5 mmol/L) was used as a linker compound and as a polydentate core compound. Tetrakis(4-aminophenyl)methane (manufactured by Tokyo Kasei Kogyo Co., Ltd.) (18.8 mmol/L) in the presence of scandium (III) triflate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) (1.5 mmol/L) as a Lewis acid catalyst.
  • terephthalaldehyde manufactured by Tokyo Chemical Industry Co., Ltd.
  • Tetrakis(4-aminophenyl)methane manufactured by Tokyo Kasei Kogyo Co., Ltd.
  • scandium (III) triflate manufactured by Tokyo Kas
  • Example 1 A resin solution was prepared by adding the above COF (b) to a polyimide precursor solution (trade name "Uimide (registered trademark)", manufactured by Unitika) and stirring. This resin solution was applied to a carrier film (trade name: “Lumirror Film (registered trademark)", manufactured by Toray Industries, Inc.). Thereafter, the carrier film coated with the resin solution was heated and dried to obtain a laminate. By removing the carrier film from this laminate, a resin film according to Example 1 was obtained. In Example 1, the resin solution was adjusted so that the content of COF (b) was 30% by volume based on the entire resin film, and the thickness of the resin film after drying was 50 ⁇ m. Next, a resin solution was applied onto the carrier film.
  • Example 2 Syndiotactic polystyrene (SPS) (trade name “Oidys (registered trademark)", manufactured by Kurabo Industries, Ltd.) is melted, and the above-mentioned COF (b) is added to the melted SPS and kneaded, thereby producing a melted resin composition. I got it.
  • the resin film according to Example 2 was obtained by applying this molten resin composition onto a continuous metal belt and peeling it off from the continuous belt after cooling.
  • SPS and COF (b) were kneaded so that the content of COF (b) was 30% by volume based on the entire resin film, and the thickness of the resin film was 50 ⁇ m.
  • the molten resin composition was applied onto a continuous metal belt so that the results were as follows.
  • Example 3 First, a liquid crystal polymer was prepared. In a reactor equipped with a stirring device, a torque meter, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, p-hydroxybenzoic acid (911 g), 4,4'-dihydroxybiphenyl (409 g), terephthalic acid (274 g), Isophthalic acid (91 g) and acetic anhydride (1235 g) were charged. After the inside of the reactor was sufficiently purged with nitrogen gas, the temperature was raised to 150° C. over 15 minutes under a nitrogen gas stream, and the temperature was maintained and refluxed for 3 hours. Then, the temperature was raised to 300° C.
  • the powdered liquid crystal polymer obtained above was melted and kneaded with the above COF (b) in a kneader to obtain a molten resin composition.
  • the resin film according to Example 3 was obtained by applying this molten resin composition onto a continuous metal belt and peeling it off from the continuous belt after cooling.
  • the liquid crystal polymer and COF (b) were kneaded so that the content of COF (b) was 30% by volume based on the entire resin film, and the thickness of the resin film was 50 ⁇ m.
  • the molten resin composition was applied onto a continuous metal belt so that the following results were obtained.
  • Example 4 By melting perfluoroalkoxyalkane (PFA) (trade name “Fulton+ (registered trademark) EA2000", manufactured by AGC), adding the above COF (b) to the melted PFA, and kneading with a kneader, A molten resin composition was obtained.
  • PFA perfluoroalkoxyalkane
  • COF COF
  • Example 4 PFA and COF(a) were kneaded so that the content of COF(a) was 10% by volume based on the entire resin film, and the thickness of the resin film was 50 ⁇ m. Next, the molten resin composition was applied onto the carrier film.
  • Example 5 to 12 Based on Table 1 shown later, the types of covalent organic frameworks (COFs) (COF(a), COF(b), COF(c)) and covalent properties for the entire resin film were determined for Example 4. Resin films were created so that at least one of the contents (volume %) of the organic framework (COF) was different. Resin films according to Examples 5 to 12 were produced in the same manner as the resin film according to Example 4 except for the type and/or content of COF.
  • COFs covalent organic frameworks
  • Example 13 A ring-opening polymer (COP) of cyclic olefin resin (trade name "ZEONOR (registered trademark)", manufactured by Nippon Zeon Co., Ltd.) is melted, the above COF (b) is added to the melted COP, and the mixture is mixed with a kneader. By kneading, a molten resin composition was obtained. This molten resin composition was applied onto a continuous metal belt, and after cooling, it was peeled off from the continuous belt to obtain a resin film according to Example 13.
  • COP ring-opening polymer
  • Example 13 COP and COF(b) were kneaded so that the content of COF(b) was 30% by volume based on the entire resin film, and the thickness of the resin film was 50 ⁇ m.
  • the molten resin composition was applied onto the carrier film so that the results were as follows.
  • Example 14 an addition polymer of norbornene monomer (polynorbornene (PNB)) was prepared. 16.4 g (0.07 mol) of 2-norbornene, 5.41 g (0.03 mol) of 5-hexyl-2-norbornene, and a polymerization solvent were placed in a reaction vessel in which the atmosphere of the polymerization system was sufficiently filled with inert gas nitrogen. 130 g of ethyl acetate and 115 g (0.53 mol) of cyclohexane were charged.
  • PPB polynorbornene
  • a catalyst solution in which 0.69 g (1.4 x 10 -3 mol) of a transition metal catalyst ( ⁇ 6-toluene nickel bis(pentafluorophenyl)) was dissolved in 5 g of toluene was charged into the reaction vessel. Stirred at room temperature for 4 hours. After polymerization, the polymerization solution was added to a mixed solution of 47 ml of glacial acetic acid, 87 ml of 30% hydrogen peroxide solution, and 300 ml of pure water, and stirred for 2 hours. The transition metal catalyst in the aqueous layer and the organic layer in the resin solution were combined.
  • Example 14 The polynorbornene obtained above was dissolved in toluene and coated on a carrier film (trade name: "Lumirror Film (registered trademark)", manufactured by Toray Industries, Inc.) to obtain a laminate. By removing the carrier film from this laminate, a resin film according to Example 14 was obtained.
  • PNB and COF(a) were kneaded so that the content of COF(a) was 10% by volume based on the entire resin film, and the thickness of the resin film was 50 ⁇ m.
  • the molten resin composition was applied onto the carrier film so that the results were as follows.
  • Example 15-22 As shown in Table 1, for Example 14, the type of covalent organic framework (COF) (COF (a), COF (b), COF (c)) and the covalent property with respect to the entire resin film Resin films were created so that at least one of the contents (volume %) of the organic framework (COF) was different. Resin films according to Examples 5 to 12 were produced in the same manner as the resin film according to Example 14 except for the type and/or content of COF.
  • COF covalent organic framework
  • Example 23 Polymethylpentene (PMP) (trade name "TPX (registered trademark)", manufactured by Mitsui Chemicals, Inc.) is melted, the above COF (b) is added to the melted PMP, and the mixture is kneaded with a kneader. A resin composition was obtained.
  • This molten resin composition was applied onto a continuous metal belt, and after cooling, it was peeled off from the continuous belt to obtain a resin film according to Example 23.
  • COP and COF (b) were kneaded so that the content of COF (b) was 30% by volume based on the entire resin film, and the thickness of the resin film was 50 ⁇ m.
  • the molten resin composition was applied onto the carrier film as shown in FIG.
  • Example 24 In the same manner as the resin film according to Example 23, except that PMP and COF (b) were kneaded so that the content of COF (b) was 50% by volume based on the entire resin film, A resin film according to Example 24 was created.
  • Example 1 A resin film was created in Example 1 without adding COF. The other production conditions were the same as in Example 1.
  • the storage modulus (E') is measured using a test piece (thickness 50 ⁇ m) obtained by cutting a resin film into a width of 9 mm and a length of 40 mm, with a measurement length (measuring jig interval) of 20 mm, and The measurement was carried out using a viscoelasticity measuring device (manufactured by TA-Instruments, RSA-G2) under the conditions of a dry air atmosphere, a temperature increase rate of 3°C/min, and a temperature range of -15°C to 300°C.
  • a viscoelasticity measuring device manufactured by TA-Instruments, RSA-G2
  • the coefficient of linear expansion (CTE) in the in-plane direction was measured for the resin films according to Examples 1 to 24 and Comparative Examples 1 to 6. Specifically, for each resin film, a 200 mm x 50 mm test piece (thickness 50 ⁇ m) was created, and the in-plane (XY direction) linear expansion was measured using the TMA (thermo-mechanical analysis) method in accordance with JIS K 7197. The coefficient was measured.
  • the TMA conditions were as follows: Using a thermal analyzer (TMA4030SA, manufactured by Bruker), the temperature was raised from room temperature to 150° C. at a rate of 10° C./min in a nitrogen atmosphere, and the load was 10 g.
  • test pieces of 200 mm x 50 mm were prepared based on the UL94 standard, and the test pieces were subjected to thin material vertical combustion according to the UL standard.
  • An evaluation test was conducted to determine flame retardancy by conducting a test (ASTM D4804).
  • Table 1 resin films whose flammability classification in the UL standard is VTM-0, VTM-1, or VTM-2 are evaluated as flame retardant, and resin films whose samples were burned out in the test are evaluated as having flame retardancy. Flame retardancy was evaluated as "none".
  • Example 1 when comparing Example 1 and Comparative Example 1, in which the resin components are both polyimide (PI), the resin film according to Comparative Example 1, which does not contain COF, has a dielectric constant of 3. Although the dielectric constant was relatively high at .8, the resin film of Example 1 containing COF had a dielectric constant of 3.0.
  • the coefficient of linear expansion (CTE) of Comparative Example 1 was less than 20 ppm/°C, and that of Example 1 was also less than 20 ppm/°C, both of which were relatively low values.
  • Example 2 when comparing Example 2 and Comparative Example 2, in which the resin components are both syndiotactic polystyrene (SPS), the resin film according to Comparative Example 2, which does not contain COF, has a relatively high CTE of 70 ppm/°C. , the resin film according to Example 2 containing COF had a CTE of 51 ppm/°C. Note that the relative permittivity of Comparative Example 2 was 2.3, and the relative permittivity of Example 2 was 2.2, both of which were relatively low values.
  • SPS syndiotactic polystyrene
  • Example 3 when comparing Example 3 and Comparative Example 3, in which the resin components are both liquid crystal polymers, it is found that the resin film according to Comparative Example 3, which does not contain COF, has a relatively high dielectric constant of 3, but the resin film containing COF The resin film according to Example 3 had a dielectric constant of 2.6. Note that the CTE of Comparative Example 3 and Example 3 were both less than 20 ppm/°C, which were relatively low values.
  • Example 13 when comparing Example 13 and Comparative Example 5, in which the resin components are both ring-opening polymers (COP) of cyclic olefin resin, the resin film according to Comparative Example 5, which does not contain COF, has a CTE of 71 ppm/°C. However, the resin film of Example 13 containing COF had a concentration of 53 ppm/°C.
  • the dielectric constant of Comparative Example 5 was 2.3, and the dielectric constant of Example 13 was 2.2, both of which were relatively low values.
  • PMP polymethylpentene
  • the COF has a mesh-like molecular skeleton that includes air with a low dielectric constant
  • the resin The dielectric constant of the composition was lower than that of the resin component.
  • the mesh-like molecular skeleton of COF is rigid because it has covalent bonds, and when the linear expansion coefficient of the resin component is relatively high, the linear expansion coefficient of the resin composition is lower than that of the resin component. became. Therefore, the resin film according to this example could be suitably used for a multilayer board.
  • this embodiment includes the following disclosures.
  • a resin film comprising a resin composition comprising a covalent organic structure in which a plurality of linker parts and a plurality of multidentate core parts are linked by covalent bonds.
  • the resin component is a thermoplastic resin
  • the water absorption rate of the resin composition is 0.1% by mass or less
  • the resin composition has a melting point of more than 300°C
  • the resin composition has a dielectric constant of less than 3.0
  • the resin film according to ⁇ 1>, wherein the resin composition has a dielectric loss tangent of less than 0.002.
  • Both ends of the linker part have carbon atoms,
  • the multidentate core portion has a nitrogen atom,
  • the resin film according to ⁇ 9>, wherein the covalent bond of the covalent organic structure is a carbon-nitrogen double bond in which a carbon atom of the linker portion and a nitrogen atom of the polydentate core portion are bonded to each other.
  • the resin film based on the present disclosure can be suitably used as a low dielectric layer included in a multilayer resin board (especially a high frequency circuit board) such as a flexible board or a rigid board.
  • Resin film 10. Covalent organic framework (COF), 11. Linker portion, 12. Multidentate core portion.
  • COF Covalent organic framework
  • Linker portion 12. Multidentate core portion.

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