Classifications

• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
  • C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
• • 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
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
• • 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
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
• • 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
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/06—Unsaturated polyesters
• • 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
  • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
  • C08J2377/12—Polyester-amides
• • 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
  • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
  • C08J2383/04—Polysiloxanes

Definitions

• the present disclosure relates to polymer films, laminates, wiring substrates, silsesquioxane polymers, and polymer compositions.
• Copper-clad laminates are preferably used as components constituting circuit boards, and films are preferably used to manufacture copper-clad laminates.
• JP 2021-27307 A describes a flexible printed circuit board including a metal layer made of one metal, a non-metallic substrate made of a material different from the material of the metal layer, a first modified silicone cured layer formed directly on the non-metallic substrate, and a second modified silicone cured layer formed directly on the metal layer, wherein both the first modified silicone cured layer and the second modified silicone cured layer contain the following chemical formula 1, and a silicone adhesive layer directly bonded to the second modified silicone cured layer and the first modified silicone cured layer, wherein the silicone adhesive layer contains the following chemical formula 2, and the first modified silicone cured layer, the second modified silicone cured layer and the silicone adhesive layer contain chemical formula 1 and chemical formula 2.
• JP 2020-185795 A describes a laminate in which a resin film and a metal foil are bonded together, in which a siloxane bond is present in the adhesive layer between the resin film and the metal foil, and the interlayer adhesive strength between the resin film and the metal foil measured in accordance with JIS K 6854-2 is 10 N/cm or more.
• JP 2021-054012 A describes a laminate for a printed wiring board, which has a substrate containing a thermoplastic resin, a modified layer located on one side of the substrate, an adhesive layer containing a thermosetting resin located on the side of the modified layer opposite the substrate, and a metal foil located on the side of the adhesive layer opposite the modified layer.
• a copper-clad laminate is manufactured by laminating a copper foil on the surface of a polymer film.
• a wiring board is manufactured by stacking a copper-clad laminate and a wiring substrate so that the film in the copper-clad laminate and the wiring substrate are in contact with each other.
• the polymer film deforms to conform to the steps formed on the surface of the wiring substrate from the viewpoint of adhesion.
• a polymer film having excellent step conformability to a wiring substrate is used for a copper-clad laminate, delamination may occur during the reflow soldering process performed when mounting electronic components. For this reason, there has been a demand for a material that has both step conformability to a wiring substrate and excellent adhesion during reflow soldering (i.e., excellent heat resistance).
• Means for solving the above problems include the following aspects.
• ⁇ 1> comprising a silsesquioxane polymer, A polymer film having a dielectric loss tangent of 0.01 or less.
• ⁇ 2> The polymer film according to ⁇ 1>, wherein the dielectric tangent is 0.005 or less.
• ⁇ 3> The polymer film according to ⁇ 1>, having a dielectric loss tangent of 0.003 or less.
• ⁇ 4> ⁇ 4> The polymer film according to any one of ⁇ 1> to ⁇ 3>, having a storage modulus at 160° C. of 0.5 MPa or less.
• ⁇ 5> The polymer film according to any one of ⁇ 1> to ⁇ 4>, wherein the storage modulus A at any temperature from 25° C. to 40° C. is 10 4 Pa to 10 8 Pa, and the storage modulus B at any temperature from 150° C. to 250° C. is 10 6 Pa or less.
• ⁇ 6> The polymer film according to ⁇ 5>, wherein the storage modulus A is 10 6 Pa to 10 8 Pa, and the storage modulus B is 3 ⁇ 10 5 Pa or less.
• ⁇ 7> The polymer film according to any one of ⁇ 1> to ⁇ 6>, wherein the silsesquioxane polymer has a crosslinkable group.
• the silsesquioxane polymer has a weight average molecular weight of 10,000 to 150,000.
• the silsesquioxane polymer includes a partial structure represented by the following formula (T2) and a partial structure represented by the following formula (T3), and a molar ratio of the partial structure represented by formula (T3) to the partial structure represented by formula (T2) is 50 or more.
• each R 1 independently represents an organic group
• X represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• ⁇ 13> The polymer film according to any one of ⁇ 1> to ⁇ 12>, having a thickness of 10 ⁇ m or more.
• ⁇ 14> The polymer film according to any one of ⁇ 1> to ⁇ 13>, which is a bonding sheet.
• ⁇ 16> The laminate according to ⁇ 15>, wherein the silsesquioxane polymer has a crosslinkable group.
• ⁇ 17> The laminate according to ⁇ 16>, wherein the crosslinkable group is at least one selected from the group consisting of a vinyl group, an allyl group, a styryl group, and a maleimide group.
• the silsesquioxane polymer includes a partial structure represented by the following formula (T2) and a partial structure represented by the following formula (T3), and a molar ratio of the partial structure represented by formula (T3) to the partial structure represented by formula (T2) is 50 or more.
• R 1 -SiO 3/2 ... (T3) R1 each independently represents an organic group
• X represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• ⁇ 20> The laminate according to any one of ⁇ 15> to ⁇ 19>, wherein the layer B further contains a thermoplastic resin or a thermosetting resin other than the silsesquioxane polymer.
• the layer B further contains an inorganic filler.
• the layer A contains a liquid crystal polymer.
• the liquid crystal polymer contains an aromatic polyester amide.
• the layer B has a thickness of 10 ⁇ m or more.
• the layer B is a polymer film according to any one of ⁇ 1> to ⁇ 14>, A laminate having a dielectric loss tangent of 0.01 or less.
• the present invention comprises a substrate, a wiring pattern disposed on at least one surface of the substrate, a layer B disposed between the wiring patterns and on the wiring patterns, and a layer A disposed on the layer B, Layer B comprises a silsesquioxane polymer; A wiring board having a dielectric loss tangent of 0.01 or less.
• the silsesquioxane polymer includes a partial structure represented by the following formula (T2a) and a partial structure represented by the following formula (T3a), and a molar ratio of the partial structure represented by formula (T3a) to the partial structure represented by formula (T2a) is 70 or more.
• R 2 -SiO 3/2 ... (T3a) In the formula, each R2 independently represents an organic group, and each R2 may be linked to another.
• X represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• ⁇ 28> The wiring board according to ⁇ 25> or ⁇ 26>, wherein the layer B further contains a thermoplastic resin or a thermosetting resin other than the silsesquioxane polymer.
• ⁇ 29> The wiring board according to any one of ⁇ 26> to ⁇ 28>, wherein the layer B further contains an inorganic filler.
• ⁇ 30> ⁇ 31> The wiring board according to any one of ⁇ 26> to ⁇ 29>, wherein the layer A contains a liquid crystal polymer.
• the liquid crystal polymer contains an aromatic polyester amide.
• the present invention comprises a substrate, a wiring pattern disposed on at least one surface of the substrate, a layer B disposed between the wiring patterns and on the wiring patterns, and a layer A disposed on the layer B,
• the layer B is a polymer film according to any one of ⁇ 1> to ⁇ 14>, A wiring board having a dielectric loss tangent of 0.01 or less.
• ⁇ 35> The silsesquioxane polymer according to ⁇ 34>, having a weight average molecular weight of 4,000 or more.
• ⁇ 36> The silsesquioxane polymer according to ⁇ 34> or ⁇ 35>, having a dielectric tangent of 0.005 or less.
• ⁇ 37> The silsesquioxane polymer according to ⁇ 34> or ⁇ 35>, having a dielectric tangent of 0.003 or less.
• the silsesquioxane polymer according to any one of ⁇ 34> to ⁇ 37> which contains a partial structure represented by the following formula (T2) and a partial structure represented by the following formula (T3), and a molar ratio of the partial structure represented by formula (T3) to the partial structure represented by formula (T2) is 50 or more.
• R1 each independently represents an organic group
• X represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• the silsesquioxane polymer according to ⁇ 38> wherein the partial structure represented by formula (T3) includes a partial structure represented by the following formula (T3k) and a partial structure represented by the following formula (T3m), and a molar ratio of the partial structure represented by formula (T3m) to the partial structure represented by formula (T3k) is 0.01 to 99.
• R 12 -SiO 3/2 ... (T3m) In formula (T3k), R 11 represents an unsubstituted aromatic hydrocarbon group, a substituted aromatic hydrocarbon group, or a vinyl group.
• R 12 is an aliphatic hydrocarbon group having a ClogP value of 2.5 or more.
• R 12 is an unsubstituted aliphatic hydrocarbon group having 4 or more carbon atoms, or an aliphatic hydrocarbon group having a substituent having 4 or more carbon atoms.
• ⁇ 41> The silsesquioxane polymer according to ⁇ 39>, wherein the molar ratio of the partial structure represented by formula (T3m) to the partial structure represented by formula (T3k) is 0.25 to 4.
• ⁇ 42> The silsesquioxane polymer according to any one of ⁇ 34> to ⁇ 41>, which has a crosslinkable group.
• ⁇ 43> The silsesquioxane polymer according to ⁇ 42>, wherein the crosslinkable group is at least one selected from the group consisting of a vinyl group, an allyl group, a styryl group, and a maleimide group.
• ⁇ 44> ⁇ 41>.
• R 11 is a styryl group
• R 12 is an unsubstituted aliphatic hydrocarbon group having 6 or more carbon atoms.
• silsesquioxane polymer according to any one of ⁇ 39> to ⁇ 42> having a storage modulus C of 10 4 Pa to 10 8 Pa at any temperature from 25° C. to 40° C., and a storage modulus D of 3 ⁇ 10 5 Pa or less at any temperature from 150° C. to 250° C. ⁇ 46> ⁇ 41>.
• a polymer composition comprising the silsesquioxane polymer according to any one of ⁇ 34> to ⁇ 46>.
• ⁇ 48> The polymer composition according to ⁇ 47>, further comprising a thermoplastic resin or a thermosetting resin other than the silsesquioxane polymer.
• ⁇ 49> The polymer composition according to ⁇ 47> or ⁇ 48>, further comprising an inorganic filler.
• a polymer film and a laminate having excellent step conformability and heat resistance are provided. Furthermore, according to another embodiment of the present invention, a wiring board is provided in which gaps around the wiring patterns are reduced and the wiring board has excellent heat resistance. According to another embodiment of the present invention, there are provided a silsesquioxane polymer and a polymer composition that can be used for a polymer film having excellent step conformability and heat resistance.
• the use of "to" indicating a range of values means that the values before and after it are included as the lower limit and upper limit.
• the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages.
• the upper or lower limit value of the numerical range may be replaced with a value shown in the examples.
• an "alkyl group” includes not only an alkyl group that has no substituents (unsubstituted alkyl groups) but also an alkyl group that has a substituent (substituted alkyl groups).
• (meth)acrylic is a term used as a concept including both acrylic and methacrylic
• (meth)acryloyl is a term used as a concept including both acryloyl and methacryloyl.
• the term "process" in this specification includes not only an independent process but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved. Furthermore, in the present disclosure, combinations of two or more preferred aspects are more preferred aspects.
• GPC gel permeation chromatography
• the polymer film according to the present disclosure comprises a silsesquioxane polymer and has a dielectric loss tangent of 0.01 or less.
• the polymer film according to the present disclosure contains a silsesquioxane polymer, which has a structure in which three oxygen atoms are bonded to a silicon atom, and is therefore considered to contribute to the step conformability and heat resistance of the polymer film.
• JP2021-27307A, JP2020-185795A, and JP2021-054012A do not contain any description focusing on silsesquioxane polymers.
• the polymer film according to the present disclosure includes a silsesquioxane polymer.
• a silsesquioxane polymer is a polymer having a structure in which one organic group and three oxygen atoms are bonded to one silicon atom, and has 13 or more silicon atoms in one molecule.
• the backbone structure of the silsesquioxane polymer is not particularly limited, and may be any of a cage structure, ladder structure, and random structure.
• the silsesquioxane polymer preferably contains at least one selected from the group consisting of a partial structure represented by the following formula (T1), a partial structure represented by the following formula (T2), and a partial structure represented by the following formula (T3).
• R 1 -SiO 3/2 ... (T3) In formulae (T1) to (T3), R1 each independently represents an organic group, and X represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• Examples of the alkyl group represented by X include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
• the number of carbon atoms in the alkyl group represented by X is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 to 3.
• Examples of the organic group represented by R 1 include a hydrocarbon group.
• the hydrocarbon group may be a group in which at least one carbon atom in a hydrocarbon group is replaced with a heteroatom (preferably an oxygen atom, a nitrogen atom, or a sulfur atom), a group in which at least one methylene group in a hydrocarbon group is replaced with a carbonyl group, or a combination thereof.
• the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
• the aliphatic hydrocarbon group may be a linear or branched saturated aliphatic hydrocarbon group, or a linear or branched unsaturated aliphatic hydrocarbon group.
• the aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, and more preferably 1 to 15.
• Examples of the aliphatic hydrocarbon group include saturated aliphatic hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl groups; and unsaturated aliphatic hydrocarbon groups such as allyl and vinyl groups.
• the aliphatic hydrocarbon group may be an alicyclic hydrocarbon group.
• the alicyclic hydrocarbon group may be an alicyclic saturated hydrocarbon group or an alicyclic unsaturated hydrocarbon group. Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, and a cyclohexenyl group.
• the aliphatic hydrocarbon group may have a substituent, which may include an aryl group, a hydroxyl group, an amino group, a thiol group, an ester group, an alkoxy group, a halogen atom, and a crosslinkable group described below.
• the aromatic hydrocarbon group preferably has 6 to 18 carbon atoms, and more preferably 6 to 14 carbon atoms.
• aromatic hydrocarbon groups include phenyl groups, naphthyl groups, and anthracenyl groups.
• the aromatic hydrocarbon group may have a substituent. Examples of the substituent in the aromatic hydrocarbon group include alkyl groups, alkoxy groups, aryl groups, hydroxyl groups, amino groups, thiol groups, halogen atoms, and vinyl groups.
• the silsesquioxane polymer preferably has a crosslinkable group, and the organic group represented by R 1 preferably contains a crosslinkable group.
• crosslinkable group examples include a vinyl group, an allyl group, a styryl group, a maleimide group, an epoxy group, and a (meth)acryloyl group.
• the crosslinkable group is at least one selected from the group consisting of a vinyl group, an allyl group, a styryl group, and a maleimide group.
• the silsesquioxane polymer contains a partial structure represented by formula (T2) and a partial structure represented by formula (T3), and the molar ratio of the partial structure represented by formula (T3) to the partial structure represented by formula (T2) is preferably 50 or more, more preferably 70 or more, even more preferably 90 or more, and particularly preferably 99 or more. There is no particular upper limit to the above molar ratio.
• the molar ratio of the partial structure represented by formula (T3) to the partial structure represented by formula (T2) is calculated from the peak area ratio of 29 Si-NMR.
• the partial structure represented by formula (T3) includes a partial structure represented by the following formula (T3k) and a partial structure represented by the following formula (T3m), and the molar ratio of the partial structure represented by formula (T3m) to the partial structure represented by formula (T3k) is 0.01 to 99.
• R 11 represents an unsubstituted aromatic hydrocarbon group, a substituted aromatic hydrocarbon group, or a vinyl group.
• R 12 is an aliphatic hydrocarbon group having a ClogP value of 2.5 or more.
• ClogP values are calculated using ChemDraw (registered trademark) Professional (ver. 16.0.1.4) from PerkinElmer Informatics.
• aromatic hydrocarbon group represented by R 11 are as described above.
• substituent that the aromatic hydrocarbon group has are as described above.
• Examples of the aliphatic hydrocarbon group having a ClogP value of 2.5 or more represented by R 12 include those having a ClogP value of 2.5 or more among the specific examples of the aliphatic hydrocarbon groups listed above.
• R 12 is preferably an unsubstituted aliphatic hydrocarbon group having 4 or more carbon atoms, or an aliphatic hydrocarbon group having a substituent having 4 or more carbon atoms.
• the number of carbon atoms in R 12 is preferably 4 to 30, and more preferably 6 to 10.
• the molar ratio of the partial structure represented by formula (T3m) to the partial structure represented by formula (T3k) is preferably 0.25 to 4, and more preferably 0.33 to 3.
• R 11 is preferably a styryl group
• R 12 is preferably an unsubstituted aliphatic hydrocarbon group having 6 or more carbon atoms.
• the difference in thermal expansion coefficient between the polymer and copper is reduced, thereby improving heat resistance.
• R 11 is a phenyl group and R 12 is an aliphatic hydrocarbon group having 6 or more carbon atoms.
• the adhesion between the polymer and copper is excellent, and therefore the heat resistance is improved.
• the storage modulus C at any temperature from 25° C. to 40° C. is preferably 10 4 Pa to 10 8 Pa
• the storage modulus D at any temperature from 150° C. to 250° C. is preferably 3 ⁇ 10 5 Pa or less.
• the storage modulus C is more preferably 10 4 Pa to 10 8 Pa over the entire temperature range from 25° C. to 40° C.
• the storage modulus D is more preferably 3 ⁇ 10 5 Pa or less over the entire temperature range from 150° C. to 250° C.
• the storage modulus C and the storage modulus D are measured in the same manner as the storage modulus at 160° C. described below.
• the storage modulus C at any temperature from 25° C. to 40° C. is 10 4 Pa to 10 8 Pa
• the storage modulus C at any temperature from 25° C. to 40° C. is 10 4 Pa to 10 8 Pa
• the measured value at any temperature from 25° C. to 40° C. is within the range of 10 4 Pa to 10 8 Pa.
• it is sufficient that the temperature at which the storage modulus is 10 4 Pa to 10 8 Pa is within the range from 25° C. to 40° C., and there may be a temperature at which the storage modulus is less than 10 4 Pa or more than 10 8 Pa.
• the storage modulus D at any temperature between 150°C and 250°C is 3 x 10 5 Pa or less
• the measured value at any temperature between 150°C and 250°C is in the range of 3 x 10 5 Pa or less.
• Whether the storage modulus C at any temperature between 25° C. and 40° C. is 10 4 Pa to 10 8 Pa can be determined by the following method. For example, when the storage modulus is continuously measured while raising the temperature at a rate of 5° C./min in the range of 25° C. to 40° C., it is determined whether the measured value falls within the range of 10 4 Pa to 10 8 Pa. Alternatively, the storage modulus may be measured at a specific temperature (for example, 25° C.) and whether the storage modulus at that temperature is 10 4 Pa to 10 8 Pa may be determined.
• the storage modulus C is more preferably 10 6 Pa to 10 8 Pa, and further preferably 5 ⁇ 10 6 Pa to 5 ⁇ 10 7 Pa.
• the storage modulus D is more preferably 10 5 Pa or less.
• the weight average molecular weight of the silsesquioxane polymer is preferably 4000 or more, more preferably 6000 to 150,000, even more preferably 10,000 to 150,000, and particularly preferably 10,000 to 100,000.
• the weight average molecular weight is 10,000 or more, the heat resistance is more excellent.
• the weight average molecular weight is 150,000 or less, the step conformability is more excellent.
• the weight average molecular weight (Mw) and number average molecular weight (Mn) of the silsesquioxane polymer in the present disclosure are molecular weights calculated using a gel permeation chromatography (GPC) analyzer equipped with a column of TSKgel Super HM-H (product name manufactured by Tosoh Corporation), detection with a differential refractometer using tetrahydrofuran as a solvent, and conversion using polystyrene as a standard substance.
• GPC gel permeation chromatography
• the content of the silsesquioxane polymer is preferably 50% by mass to 100% by mass, and more preferably 60% by mass to 90% by mass, based on the total mass of the polymer film.
• the polymer film according to the present disclosure preferably further contains a thermoplastic resin or a thermosetting resin other than the silsesquioxane polymer.
• the thermoplastic resin may be a thermoplastic elastomer.
• An elastomer is a polymeric compound that exhibits elastic deformation. In other words, it is a polymeric compound that has the property of deforming in response to the application of an external force and recovering to its original shape in a short time when the external force is removed.
• Thermoplastic resins include polyurethane resins, polyester resins, (meth)acrylic resins, polystyrene resins, fluororesins, polyimide resins, fluorinated polyimide resins, polyamide resins, polyamideimide resins, polyetherimide resins, cellulose acylate resins, polyurethane resins, polyether ether ketone resins, polycarbonate resins, polyolefin resins (e.g., polyethylene resins, polypropylene resins, resins made of cyclic olefin copolymers, alicyclic polyolefin resins), polyarylate resins, polyethersulfone resins, polysulfone resins, fluorene ring-modified polycarbonate resins, alicyclic modified polycarbonate resins, and fluorene ring-modified polyester resins.
• polyolefin resins e.g., polyethylene resins, polypropylene resins, resin
• Thermoplastic elastomers are not particularly limited, and examples include elastomers containing repeating units derived from styrene (polystyrene-based elastomers), polyester-based elastomers, polyolefin-based elastomers, polyurethane-based elastomers, polyamide-based elastomers, polyacrylic-based elastomers, silicone-based elastomers, polyimide-based elastomers, etc.
• the thermoplastic elastomers may be hydrogenated.
• Polystyrene-based elastomers include styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), polystyrene-poly(ethylene-propylene) diblock copolymers (SEP), polystyrene-poly(ethylene-propylene)-polystyrene triblock copolymers (SEPS), styrene-ethylene-butylene-styrene block copolymers (SEBS), polystyrene-poly(ethylene/ethylene-propylene)-polystyrene triblock copolymers (SEEPS), styrene-isobutylene-styrene block copolymers (SIBS), and hydrogenated versions of these.
• SBS styrene-butadiene-styrene block copolymers
• SIS
• the polymer film according to the present disclosure preferably contains a thermoplastic resin containing a structural unit derived from a monomer having an aromatic hydrocarbon group, more preferably contains a polystyrene-based elastomer, and more preferably contains a styrene-ethylene-butylene-styrene block copolymer, or a styrene-isobutylene-styrene block copolymer, a styrene-ethylene-propylene block copolymer, a styrene-ethylene-propylene-styrene block copolymer, or a styrene-ethylene-ethylene-propylene-styrene copolymer.
• thermosetting resins examples include epoxy resins, oxazine resins, bismaleimide resins, phenolic resins, unsaturated polyester resins, and silicone resins.
• thermoplastic resin or thermosetting resin other than the silsesquioxane polymer is not particularly limited, but from the viewpoints of dielectric tangent, heat resistance, and step conformability, it is preferably 5% by mass to 50% by mass, and more preferably 10% by mass to 40% by mass, relative to the total mass of the polymer film.
• the polymer film according to the present disclosure preferably contains a filler from the viewpoints of dielectric tangent, heat resistance, and step conformability.
• the filler may be particulate or fibrous, and may be an inorganic filler or an organic filler. From the viewpoints of dielectric tangent, heat resistance, and step conformability, it is preferable that the polymer film according to the present disclosure contains an inorganic filler.
• organic filler a known organic filler can be used.
• the organic filler material include polyethylene, polystyrene, urea-formalin filler, polyester, cellulose, acrylic resin, fluororesin, hardened epoxy resin, crosslinked benzoguanamine resin, crosslinked acrylic resin, liquid crystal polymer, and materials containing two or more of these.
• the organic filler may also be in the form of fibers such as nanofibers, or may be hollow resin particles.
• the organic filler is preferably fluororesin particles, polyester resin particles, polyethylene particles, liquid crystal polymer particles, or nanofibers of cellulose resin, more preferably polytetrafluoroethylene particles, polyethylene particles, or liquid crystal polymer particles, and particularly preferably liquid crystal polymer particles.
• the liquid crystal polymer particles refer to, but are not limited to, liquid crystal polymer particles obtained by polymerizing liquid crystal polymer and pulverizing it with a pulverizer or the like to obtain powdered liquid crystal. It is preferable that the liquid crystal polymer particles are smaller than the thickness of each layer.
• the average particle size of the organic filler is preferably 5 nm to 20 ⁇ m, and more preferably 100 nm to 10 ⁇ m, from the viewpoints of dielectric tangent, heat resistance, and step conformability.
• the inorganic filler a known inorganic filler can be used.
• the inorganic filler material include BN, Al2O3 , AlN, TiO2 , SiO2 , barium titanate , strontium titanate, aluminum hydroxide, calcium carbonate, and materials containing two or more of these.
• metal oxide particles or fibers are preferred, silica particles, titania particles, or glass fibers are more preferred, and silica particles or glass fibers are particularly preferred.
• the average particle size of the inorganic filler is preferably about 20% to about 40% of the thickness of the film, and may be, for example, 25%, 30%, or 35% of the thickness of the film.
• the length indicates the length in the short side direction.
• the average particle size of the inorganic filler is preferably 5 nm to 20 ⁇ m, more preferably 10 nm to 10 ⁇ m, even more preferably 20 nm to 1 ⁇ m, and particularly preferably 25 nm to 500 nm.
• the polymer film according to the present disclosure may contain only one type of filler, or may contain two or more types of fillers.
• the content of the filler is preferably 5% by mass to 50% by mass, and more preferably 10% by mass to 40% by mass, relative to the total mass of the polymer film, from the viewpoints of the dielectric tangent, heat resistance, and step conformability of the polymer film.
• the polymer film according to the present disclosure preferably contains a polymerization initiator in order to crosslink the silsesquioxane polymers together.
• the polymerization initiator is preferably a thermal radical polymerization initiator that generates radicals by heating.
• thermal radical polymerization initiators include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(N-butyl-2-methylpropionamide), dimethyl-1,1'-azobis(1-cyclohexanecarboxylate), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride; 1,1-di(t-hexyl)azobis[2-(2-imidazolin-2-yl)propane
• the amount of the polymerization initiator is not particularly limited, but from the viewpoint of curability, it is preferably 0.1% by mass to 10% by mass, and more preferably 1% by mass to 5% by mass, relative to the total mass of the polymer film.
• the polymer film according to the present disclosure may contain additives other than the above-mentioned components.
• additives known additives can be used, specifically, for example, curing agents, leveling agents, antifoaming agents, antioxidants, ultraviolet absorbing agents, flame retardants, colorants, etc.
• the average thickness of the polymer film according to the present disclosure is preferably 10 ⁇ m or more, more preferably 15 ⁇ m to 40 ⁇ m, and even more preferably 20 ⁇ m to 30 ⁇ m, from the viewpoints of heat resistance and conformability to uneven surfaces.
• the dielectric loss tangent of the polymer film according to the present disclosure is 0.01 or less, preferably 0.006 or less, more preferably 0.005 or less, and even more preferably 0.003 or less.
• the dielectric loss tangent of the polymer film according to the present disclosure is preferably greater than 0 and less than 0.004, and even more preferably greater than 0 and less than 0.003.
• the dielectric tangent is measured by the following method.
• the dielectric loss tangent is measured by a resonance perturbation method at a frequency of 28 GHz.
• a 28 GHz cavity resonator (Kanto Electronics Application Development Co., Ltd., CP531) is connected to a network analyzer (Agilent Technology, Inc., E8363B), a measurement sample is inserted into the cavity resonator, and the change in resonance frequency is measured before and after insertion for 96 hours under an environment of 25°C temperature and 60% RH.
• the storage modulus of the polymer film according to the present disclosure at 160°C is preferably 0.5 MPa or less, and more preferably 0.3 MPa or less.
• the lower limit of the storage modulus it is preferably 0.01 MPa. It is more preferable that the storage modulus at 160°C be 0.05 MPa to 0.5 MPa.
• the storage modulus of a polymer film at 160°C is measured by the following method.
• the polymer film according to the present disclosure preferably has a storage modulus A of 10 4 Pa to 10 8 Pa at any temperature from 25° C. to 40° C., and preferably has a storage modulus B of 10 6 Pa or less at any temperature from 150° C. to 250° C.
• the storage modulus A is 10 4 Pa to 10 8 Pa over the entire temperature range from 25° C. to 40° C.
• the storage modulus B is 10 6 Pa or less over the entire temperature range from 150° C. to 250° C.
• the storage elastic modulus A and the storage elastic modulus B are measured in the same manner as the storage elastic modulus at 160° C. described above. "The storage modulus A at any temperature between 25°C and 40°C is 10 4 Pa to 10 8 Pa” means that the measured value at any temperature between 25°C and 40°C falls within the range of 10 4 Pa to 10 8 Pa. Similarly, “the storage modulus B at any temperature between 150°C and 250°C is 10 6 Pa or less” means that the measured value at any temperature between 150°C and 250°C is in the range of 10 6 Pa or less.
• the polymer film according to the present disclosure more preferably has a storage modulus A of 10 6 Pa to 10 8 Pa, and a storage modulus B of 3 ⁇ 10 5 Pa or less. From the viewpoint of adhesion to metals (particularly copper), the polymer film according to the present disclosure more preferably has a storage modulus A of 5 ⁇ 10 6 Pa to 5 ⁇ 10 7 Pa, and even more preferably has a storage modulus B of 10 5 Pa or less.
• the polymer film according to the present disclosure is preferably a bonding sheet.
• a bonding sheet is a sheet that is used by being attached to another substrate and has an adhesive function.
• the laminate according to the present disclosure includes a layer A and a layer B disposed on at least one surface of the layer A, the layer B including a silsesquioxane polymer and having a dielectric loss tangent of 0.01 or less. Furthermore, the laminate according to the present disclosure includes a layer A and a layer B disposed on at least one surface of the layer A, and the layer B may be a polymer film according to the present disclosure.
• the laminate according to the present disclosure contains a silsesquioxane polymer, so that Layer B functions as a step-conforming layer and has excellent step-conforming properties.
• the silsesquioxane polymer has a structure in which three oxygen atoms are bonded to a silicon atom, which is thought to contribute to the heat resistance of the laminate.
• Patent Documents 1 to 3 do not include any description that focuses on silsesquioxane polymers.
• the laminate according to the present disclosure has a layer A on which a layer B described below is provided. From the viewpoint of making the dielectric loss tangent of the laminate 0.01 or less, the layer A preferably contains a polymer having a dielectric loss tangent of 0.01 or less.
• Layer A may contain only one type of polymer with a dielectric tangent of 0.01 or less, or may contain two or more types.
• the dielectric tangent of a polymer having a dielectric tangent of 0.01 or less is preferably 0.006 or less, from the viewpoint of the dielectric tangent of the laminate, and more preferably is greater than 0 and less than 0.004.
• polymers with a dielectric tangent of 0.01 or less include liquid crystal polymers, fluororesins, polymers of compounds having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond, thermoplastic resins such as polyether ether ketone, polyolefin, polyamide, polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyether sulfone, polyphenylene ether and modified products thereof, and polyether imide; elastomers such as copolymers of glycidyl methacrylate and polyethylene; and thermosetting resins such as phenol resins, epoxy resins, polyimides, and cyanate resins.
• thermoplastic resins such as polyether ether ketone, polyolefin, polyamide, polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyether sulfone, polyphenylene ether and modified products thereof, and polyether
• the polymer having a dielectric loss tangent of 0.01 or less is preferably a liquid crystal polymer, that is, Layer A preferably contains a liquid crystal polymer.
• the type of liquid crystal polymer is not particularly limited, and any known liquid crystal polymer can be used.
• the liquid crystal polymer may be a thermotropic liquid crystal polymer that exhibits liquid crystallinity in a molten state, or a lyotropic liquid crystal polymer that exhibits liquid crystallinity in a solution state. In the case of a thermotropic liquid crystal, it is preferable that the liquid crystal polymer melts at a temperature of 450° C. or less.
• liquid crystal polymers examples include liquid crystal polyester, liquid crystal polyester amide in which an amide bond has been introduced into liquid crystal polyester, liquid crystal polyester ether in which an ether bond has been introduced into liquid crystal polyester, and liquid crystal polyester carbonate in which a carbonate bond has been introduced into liquid crystal polyester.
• the liquid crystal polymer is preferably a polymer having an aromatic ring, and is more preferably an aromatic polyester or an aromatic polyester amide.
• the liquid crystal polymer may be a polymer in which an isocyanate-derived bond such as an imide bond, a carbodiimide bond, or an isocyanurate bond has been introduced into an aromatic polyester or an aromatic polyester amide.
• an isocyanate-derived bond such as an imide bond, a carbodiimide bond, or an isocyanurate bond has been introduced into an aromatic polyester or an aromatic polyester amide.
• liquid crystal polymer is preferably a fully aromatic liquid crystal polymer made using only aromatic compounds as raw material monomers.
• liquid crystal polymer examples include the following liquid crystal polymers. 1) A compound obtained by polycondensation of (i) an aromatic hydroxycarboxylic acid, (ii) an aromatic dicarboxylic acid, and (iii) at least one compound selected from the group consisting of an aromatic diol, an aromatic hydroxyamine, and an aromatic diamine. 2) Those obtained by polycondensation of multiple types of aromatic hydroxycarboxylic acids. 3) (i) a polycondensation product of an aromatic dicarboxylic acid and (ii) at least one compound selected from the group consisting of an aromatic diol, an aromatic hydroxyamine and an aromatic diamine.
• Polyester such as polyethylene terephthalate
• aromatic hydroxycarboxylic acid are polycondensed.
• the aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic hydroxyamine and aromatic diamine may each independently be replaced with a derivative capable of undergoing polycondensation.
• the melting point of the liquid crystal polymer is preferably 250°C or higher, more preferably 250°C to 350°C, and even more preferably 260°C to 330°C.
• the melting point is measured using a differential scanning calorimeter.
• a differential scanning calorimeter For example, it is measured using a product called "DSC-60A Plus" (manufactured by Shimadzu Corporation).
• the heating rate in the measurement is 10°C/min.
• the weight average molecular weight of the liquid crystal polymer is preferably 1,000,000 or less, more preferably 3,000 to 300,000, even more preferably 5,000 to 100,000, and particularly preferably 5,000 to 30,000.
• the liquid crystal polymer preferably contains an aromatic polyesteramide from the viewpoint of further reducing the dielectric tangent.
• An aromatic polyesteramide is a resin having at least one aromatic ring and having an ester bond and an amide bond.
• the aromatic polyesteramide is preferably a fully aromatic polyesteramide.
• the aromatic polyester amide is preferably a crystalline polymer.
• the layer A preferably contains a crystalline aromatic polyester amide.
• the aromatic polyester amide contained in the layer A is crystalline, the dielectric tangent is further reduced.
• crystalline polymer refers to a polymer that has a clear endothermic peak, not a stepwise change in endothermic amount, in differential scanning calorimetry (DSC). Specifically, for example, it means that the half-width of the endothermic peak is within 10° C. when measured at a heating rate of 10° C./min. Polymers with a half-width exceeding 10° C. and polymers without a clear endothermic peak are classified as amorphous polymers and are distinguished from crystalline polymers.
• the aromatic polyester amide preferably contains a constitutional unit represented by the following formula 1, a constitutional unit represented by the following formula 2, and a constitutional unit represented by the following formula 3. -O-Ar 1 -CO- ... Formula 1 -CO-Ar 2 -CO- ... Formula 2 —NH—Ar 3 —O— Formula 3
• Ar 1 , Ar 2 and Ar 3 each independently represent a phenylene group, a naphthylene group or a biphenylylene group.
• the structural unit represented by formula 1 will also be referred to as "unit 1", etc.
• the unit 1 can be introduced, for example, by using an aromatic hydroxycarboxylic acid as a raw material.
• the unit 2 can be introduced, for example, by using an aromatic dicarboxylic acid as a raw material.
• Unit 3 can be introduced, for example, by using an aromatic hydroxylamine as a raw material.
• aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, and aromatic hydroxylamine may each be independently replaced with a derivative capable of polycondensation.
• aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid esters and aromatic dicarboxylic acid esters by converting the carboxy group to an alkoxycarbonyl group or an aryloxycarbonyl group.
• Aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid halides and aromatic dicarboxylic acid halides by converting the carboxy groups to haloformyl groups.
• Aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced by aromatic hydroxycarboxylic acid anhydrides and aromatic dicarboxylic acid anhydrides by converting the carboxy groups to acyloxycarbonyl groups.
• polycondensable derivatives of compounds having a hydroxy group such as aromatic hydroxycarboxylic acids and aromatic hydroxyamines
• examples of polycondensable derivatives of compounds having a hydroxy group include those obtained by acylation of a hydroxy group into an acyloxy group (acylated products).
• aromatic hydroxycarboxylic acids and aromatic hydroxylamines can be replaced with their acylated counterparts by acylation of the hydroxy group to convert it to an acyloxy group.
• polycondensable derivatives of aromatic hydroxylamines include those obtained by acylation of the amino group to an acylamino group (acylated product).
• aromatic hydroxyamines can be replaced with acylated products by converting the amino group into an acylamino group through acylation.
• Ar 1 is preferably a p-phenylene group, a 2,6-naphthylene group, or a 4,4'-biphenylylene group, and more preferably a 2,6-naphthylene group.
• unit 1 is, for example, a constitutional unit derived from p-hydroxybenzoic acid.
• unit 1 is, for example, a constitutional unit derived from 6-hydroxy-2-naphthoic acid.
• Ar 1 is a 4,4'-biphenylylene group
• unit 1 is, for example, a constitutional unit derived from 4'-hydroxy-4-biphenylcarboxylic acid.
• Ar 2 is preferably a p-phenylene group, an m-phenylene group, or a 2,6-naphthylene group, and more preferably an m-phenylene group.
• unit 2 is, for example, a constitutional unit derived from terephthalic acid.
• unit 2 is, for example, a constitutional unit derived from isophthalic acid.
• Ar 2 is a 2,6-naphthylene group
• unit 2 is, for example, a constitutional unit derived from 2,6-naphthalenedicarboxylic acid.
• Ar 3 is preferably a p-phenylene group or a 4,4′-biphenylylene group, and more preferably a p-phenylene group.
• unit 3 is, for example, a constitutional unit derived from p-aminophenol.
• unit 3 is, for example, a constitutional unit derived from 4-amino-4'-hydroxybiphenyl.
• the content of units 1 is preferably 30 mol % or more, the content of units 2 is preferably 35 mol % or less, and the content of units 3 is preferably 35 mol % or less.
• the content of unit 1 is more preferably 30 mol % to 80 mol %, further preferably 30 mol % to 60 mol %, and particularly preferably 30 mol % to 40 mol %, based on the total content of unit 1, unit 2, and unit 3.
• the content of unit 2 is preferably 10 mol % to 35 mol %, more preferably 20 mol % to 35 mol %, and particularly preferably 30 mol % to 35 mol %, based on the total content of unit 1, unit 2, and unit 3.
• the content of unit 3 is preferably 10 mol % to 35 mol %, more preferably 20 mol % to 35 mol %, and particularly preferably 30 mol % to 35 mol %, based on the total content of unit 1, unit 2, and unit 3.
• the total content of each structural unit is the sum of the amounts (moles) of each structural unit, which is calculated by dividing the mass of each structural unit constituting the aromatic polyesteramide by the formula weight of the structural unit.
• the ratio of the content of unit 2 to the content of unit 3, expressed as [content of unit 2]/[content of unit 3] (mol/mol), is preferably 0.9/1 to 1/0.9, more preferably 0.95/1 to 1/0.95, and even more preferably 0.98/1 to 1/0.98.
• the aromatic polyesteramide may have two or more types of units 1 to 3, each of which is independent.
• the aromatic polyesteramide may also have other structural units in addition to units 1 to 3.
• the content of the other structural units is preferably 10 mol % or less, more preferably 5 mol % or less, based on the total content of all structural units.
• Aromatic polyesteramides are preferably produced by melt polymerizing raw material monomers that correspond to the structural units that make up the aromatic polyesteramide.
• the weight average molecular weight of the aromatic polyester amide is preferably 1,000,000 or less, more preferably 3,000 to 300,000, even more preferably 5,000 to 100,000, and particularly preferably 5,000 to 30,000.
• the polymer having a dielectric loss tangent of 0.01 or less may be a fluororesin from the viewpoints of heat resistance and mechanical strength.
• the type of fluororesin is not particularly limited, and any known fluororesin can be used.
• Fluororesins include homopolymers and copolymers that contain structural units derived from fluorinated ⁇ -olefin monomers, i.e., ⁇ -olefin monomers that contain at least one fluorine atom. Fluororesins also include copolymers that contain structural units derived from fluorinated ⁇ -olefin monomers and structural units derived from non-fluorinated ethylenically unsaturated monomers that are reactive with fluorinated ⁇ -olefin monomers.
• Fluorinated ⁇ -olefin monomers include CF 2 ⁇ CF 2 , CHF ⁇ CF 2 , CH 2 ⁇ CF 2 , CHCl ⁇ CHF, CCIF ⁇ CF 2 , CCl 2 ⁇ CF 2 , CCIF ⁇ CCIF, CHF ⁇ CCl 2 , CH 2 ⁇ CCIF, CCl 2 ⁇ CCIF, CF 3 CF ⁇ CF 2 , CF 3 CF ⁇ CHF, CF 3 CH ⁇ CF 2 , CHF 2 CH ⁇ CHF, CF 3 CF ⁇ CF 2 , and perfluoro ( alkyl having 2 to 8 carbon atoms)vinyl ethers (e.g., perfluoromethyl vinyl ether, perfluoropropyl vinyl ether, and perfluorooctyl vinyl ether ) .
• perfluoro ( alkyl having 2 to 8 carbon atoms)vinyl ethers e.g., perfluoromethyl vinyl ether, perfluoropropyl
• the fluorinated ⁇ -olefin monomer is preferably at least one monomer selected from the group consisting of tetrafluoroethylene (CF 2 ⁇ CF 2 ), chlorotrifluoroethylene (CCIF ⁇ CF 2 ), (perfluorobutyl)ethylene, vinylidene fluoride (CH 2 ⁇ CF 2 ), and hexafluoropropylene (CF 2 ⁇ CFCF 3 ).
• Non-fluorinated ethylenically unsaturated monomers include ethylene, propylene, butene, ethylenically unsaturated aromatic monomers (eg, styrene and ⁇ -methylstyrene), and the like.
• the fluorinated ⁇ -olefin monomers may be used alone or in combination of two or more kinds.
• the non-fluorinated ethylenically unsaturated monomers may be used alone or in combination of two or more kinds.
• fluororesins include polychlorotrifluoroethylene (PCTFE), poly(chlorotrifluoroethylene-propylene), poly(ethylene-tetrafluoroethylene) (ETFE), poly(ethylene-chlorotrifluoroethylene) (ECTFE), poly(hexafluoropropylene), poly(tetrafluoroethylene) (PTFE), poly(tetrafluoroethylene-ethylene-propylene), poly(tetrafluoroethylene-hexafluoropropylene) (FEP), poly(tetrafluoroethylene-propylene) (FEPM), poly(tetrafluoroethylene-perfluoropropylene vinyl ether), poly(tetrafluoroethylene-perfluoroalkyl vinyl ether) (PFA) (e.g., poly(tetrafluoroethylene-perfluoropropyl vinyl ether)), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), poly((
• the fluororesin may have a structural unit derived from fluorinated ethylene or fluorinated propylene.
• the fluororesin may be used alone or in combination of two or more kinds.
• the fluororesin is preferably FEP, PFA, ETFE, or PTFE.
• FEP is available from DuPont under the trade name TEFLON FEP, or from Daikin Industries, Ltd. under the trade name NEOFLON FEP.
• PFA is available from Daikin Industries, Ltd. under the trade name NEOFLON PFA, from DuPont under the trade name TEFLON PFA, or from Solvay Solexis under the trade name HYFLON PFA.
• the fluororesin contains PTFE.
• the PTFE may be a PTFE homopolymer, a partially modified PTFE homopolymer, or a combination containing one or both of these.
• the partially modified PTFE homopolymer preferably contains less than 1% by mass of structural units derived from comonomers other than tetrafluoroethylene, based on the total mass of the polymer.
• the fluororesin may be a crosslinkable fluoropolymer having a crosslinkable group.
• the crosslinkable fluoropolymer can be crosslinked by a conventionally known crosslinking method.
• One representative crosslinkable fluoropolymer is a fluoropolymer having (meth)acryloyloxy.
• R is an oligomer chain containing constitutional units derived from a fluorinated ⁇ -olefin monomer
• R′ is H or —CH3
• n is 1 to 4.
• R may also be a fluorine-based oligomer chain containing constitutional units derived from tetrafluoroethylene.
• a crosslinked fluoropolymer network can be formed by exposing a fluoropolymer having (meth)acryloyloxy groups to a free radical source to initiate a radical crosslinking reaction via the (meth)acryloyloxy groups on the fluororesin.
• the free radical source is not particularly limited, but suitable examples include a photoradical polymerization initiator or an organic peroxide. Suitable photoradical polymerization initiators and organic peroxides are well known in the art.
• Crosslinkable fluoropolymers are commercially available, such as Viton B manufactured by DuPont.
• the polymer having a dielectric loss tangent of 0.01 or less may be a polymer of a compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond.
• polymers of compounds having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond include thermoplastic resins having structural units derived from cyclic olefin monomers such as norbornene or polycyclic norbornene monomers.
• the polymer of a compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be a ring-opening polymer of the above-mentioned cyclic olefin or a hydrogenated product of a ring-opening copolymer using two or more kinds of cyclic olefins, or may be an addition polymer of a cyclic olefin and an aromatic compound having an ethylenically unsaturated bond such as a chain olefin or a vinyl group.
• a polar group may be introduced into the polymer of a compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond.
• the polymer of the compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be used alone or in combination of two or more types.
• the ring structure of the cyclic aliphatic hydrocarbon group may be a monocyclic ring, a condensed ring in which two or more rings are condensed, or a bridged ring.
• Examples of the ring structure of the cyclic aliphatic hydrocarbon group include a cyclopentane ring, a cyclohexane ring, a cyclooctane ring, an isoborone ring, a norbornane ring, and a dicyclopentane ring.
• the compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond is not particularly limited, and may be a (meth)acrylate compound having a cyclic aliphatic hydrocarbon group, a (meth)acrylamide compound having a cyclic aliphatic hydrocarbon group, or a vinyl compound having a cyclic aliphatic hydrocarbon group. Among them, a (meth)acrylate compound having a cyclic aliphatic hydrocarbon group is preferably used.
• the compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be a monofunctional ethylenically unsaturated compound or a polyfunctional ethylenically unsaturated compound.
• the number of cycloaliphatic hydrocarbon groups in the compound having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be one or more, and may be two or more.
• the polymer of a compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be a polymer obtained by polymerizing a compound having at least one type of cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond, and may be a polymer of a compound having two or more types of cyclic aliphatic hydrocarbon groups and a group having an ethylenically unsaturated bond, or may be a copolymer with another ethylenically unsaturated compound that does not have a cyclic aliphatic hydrocarbon group.
• the polymer of a compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond is preferably a cycloolefin polymer.
• the polymer having a dielectric loss tangent of 0.01 or less may be a polyphenylene ether.
• the polyphenylene ether preferably has an average number of phenolic hydroxyl groups at the molecular terminals per molecule (number of terminal hydroxyl groups) of 1 to 5, and more preferably 1.5 to 3, from the viewpoints of dielectric tangent and heat resistance.
• the number of terminal hydroxyl groups of polyphenylene ether can be known from, for example, the specification value of the polyphenylene ether product.
• the number of terminal hydroxyl groups is expressed, for example, as the average number of phenolic hydroxyl groups per molecule of all polyphenylene ethers present in 1 mole of polyphenylene ether.
• the polyphenylene ether may be used alone or in combination of two or more kinds.
• polyphenylene ethers examples include polyphenylene ethers made of 2,6-dimethylphenol and at least one of a difunctional phenol and a trifunctional phenol, and poly(2,6-dimethyl-1,4-phenylene oxide). More specifically, the polyphenylene ether is preferably a compound having a structure represented by the formula (PPE).
• X represents an alkylene group having 1 to 3 carbon atoms or a single bond
• m represents an integer of 0 to 20
• n represents an integer of 0 to 20
• the sum of m and n represents an integer of 1 to 30.
• the alkylene group for X is, for example, a dimethylmethylene group.
• the weight average molecular weight (Mw) is preferably 500 to 5,000, and more preferably 500 to 3,000, from the viewpoints of heat resistance and film formability. If the polyphenylene ether is not thermally cured, the weight average molecular weight (Mw) is not particularly limited, but is preferably 3,000 to 100,000, and more preferably 5,000 to 50,000.
• Aromatic polyether ketone The polymer having a dielectric loss tangent of 0.01 or less may be an aromatic polyether ketone.
• the aromatic polyether ketone is not particularly limited, and any known aromatic polyether ketone can be used.
• the aromatic polyether ketone is preferably polyether ether ketone.
• Polyetheretherketone is a type of aromatic polyetherketone, and is a polymer in which bonds are arranged in the following order: ether bond, ether bond, and carbonyl bond. Each bond is preferably linked by a divalent aromatic group.
• the aromatic polyether ketones may be used alone or in combination of two or more kinds.
• aromatic polyetherketones examples include polyetheretherketone (PEEK) having a chemical structure represented by the following formula (P1), polyetherketone (PEK) having a chemical structure represented by the following formula (P2), polyetherketoneketone (PEKK) having a chemical structure represented by the following formula (P3), polyetheretherketoneketone (PEEKK) having a chemical structure represented by the following formula (P4), and polyetherketoneetherketoneketone (PEKEKK) having a chemical structure represented by the following formula (P5).
• n in each of formulas (P1) to (P5) is preferably 10 or more, and more preferably 20 or more.
• n is preferably 5,000 or less, and more preferably 1,000 or less. In other words, n is preferably 10 to 5,000, and more preferably 20 to 1,000.
• the content of the polymer having a dielectric tangent of 0.01 or less is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 20% by mass to 100% by mass, relative to the total mass of Layer A.
• the polymer with a dielectric tangent of 0.01 or less is a liquid crystal polymer, from the viewpoint of the dielectric tangent of the laminate, it is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 20% by mass to 50% by mass, of the total mass of Layer A.
• Layer A may contain a filler in addition to the polymer having a dielectric tangent of 0.01 or less.
• the filler may be particulate or fibrous, and may be an inorganic filler or an organic filler. Specific examples of the inorganic filler and the organic filler are as described above.
• the filler contained in layer A is preferably an organic filler, and more preferably liquid crystal polymer particles, from the viewpoints of the dielectric tangent, heat resistance, and step conformability of the laminate.
• Layer A may contain only one type of filler, or may contain two or more types of fillers.
• the content of the filler is preferably 30% by mass to 95% by mass, more preferably 50% by mass to 90% by mass, and particularly preferably 60% by mass to 80% by mass, relative to the total mass of Layer A, from the viewpoints of the dielectric tangent, heat resistance, and step-following ability of the laminate.
• Layer A may contain additives other than the above-mentioned components. Preferred aspects of other additives that may be contained in Layer A are the same as preferred aspects of other additives that may be contained in the polymer film according to the present disclosure.
• the layer A may contain, as other additives, resins other than the polymer having a dielectric loss tangent of 0.01 or less.
• resins other than polymers having a dielectric tangent of 0.01 or less include thermoplastic resins other than liquid crystal polyesters, such as polypropylene, polyamide, polyesters other than liquid crystal polyesters, polyphenylene sulfide, polyether ketone, polycarbonate, polyether sulfone, polyphenylene ether and modified products thereof, and polyether imide; elastomers such as copolymers of glycidyl methacrylate and polyethylene; and thermosetting resins such as phenol resins, epoxy resins, polyimide resins, and cyanate resins.
• the total content of other additives in Layer A is preferably 25 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less, per 100 parts by mass of the polymer having a dielectric tangent of 0.01 or less.
• the average thickness of layer A is not particularly limited, but from the viewpoint of the dielectric tangent, heat resistance, and step conformability of the laminate, it is preferably 5 ⁇ m to 90 ⁇ m, more preferably 10 ⁇ m to 70 ⁇ m, and particularly preferably 15 ⁇ m to 50 ⁇ m.
• the method for measuring the average thickness of each layer in the laminate according to the present disclosure is as follows.
• the laminate is cut on a plane perpendicular to the in-plane direction of the laminate, the thickness is measured at five or more points on the cross section, and the average of these measurements is taken as the average thickness.
• the dielectric tangent of layer A is preferably 0.01 or less, more preferably 0.005 or less, and even more preferably greater than 0 and 0.003 or less.
• the laminate according to the present disclosure has a layer B on at least one surface of the layer A.
• the layer B is preferably a surface layer (outermost layer).
• Layer B contains a silsesquioxane polymer.
• a preferred embodiment of the silsesquioxane polymer contained in layer B is the same as a preferred embodiment of the silsesquioxane polymer contained in the polymer film according to the present disclosure.
• Layer B further contains a thermoplastic resin or a thermosetting resin other than the silsesquioxane polymer.
• the preferred aspects of the thermoplastic resin and the thermosetting resin that may be contained in Layer B are the same as the preferred aspects of the thermoplastic resin and the thermosetting resin that may be contained in the polymer film according to the present disclosure.
• Layer B contains a filler from the viewpoints of the dielectric tangent, heat resistance, and step conformability of the laminate.
• Preferred embodiments of the filler that may be contained in Layer B are the same as preferred embodiments of the filler that may be contained in the polymer film of the present disclosure.
• layer B contains a polymerization initiator in order to crosslink the silsesquioxane polymers.
• the preferred embodiment of the polymerization initiator that may be contained in layer B is the same as the preferred embodiment of the polymerization initiator that may be contained in the polymer film according to the present disclosure.
• Layer B may contain additives other than those mentioned above. Preferred embodiments of other additives that may be contained in Layer B are the same as preferred embodiments of other additives that may be contained in the polymer film according to the present disclosure.
• Layer B is preferably the surface layer (outermost layer). Layer B has excellent step conformability, and therefore has excellent adhesion when bonded to metal wiring.
• the average thickness of Layer B is preferably 10 ⁇ m or more, more preferably 15 ⁇ m to 40 ⁇ m, and even more preferably 20 ⁇ m to 30 ⁇ m.
• the dielectric tangent of layer B is preferably 0.01 or less, more preferably 0.006 or less, and even more preferably greater than 0 and 0.004 or less.
• the elastic modulus of layer B at 160°C is preferably 0.5 MPa or less, and more preferably 0.3 MPa or less. There are no particular limitations on the lower limit of the elastic modulus, but from the viewpoint of heat resistance, it is preferably 0.01 MPa.
• the elastic modulus of layer B at 160°C is measured by the following method.
• the laminate is cut into a cross section using a microtome or the like, and layer B is identified from the image observed under an optical microscope.
• the elastic modulus of the identified layer B is measured as the indentation elastic modulus using the nanoindentation method.
• the indentation elastic modulus is measured using a microhardness tester (product name "DUH-W201", manufactured by Shimadzu Corporation) at 160°C by applying a load with a Vickers indenter at a loading rate of 0.28 mN/sec, holding the maximum load of 10 mN for 10 seconds, and then unloading at a loading rate of 0.28 mN/sec.
• the laminate according to the present disclosure preferably further comprises layer C in addition to layer A and layer B, and more preferably comprises layer B, layer A, and layer C in this order.
• Layer C is preferably an adhesive layer, i.e., Layer C is preferably a surface layer (outermost layer).
• layer C contains at least one type of polymer.
• the preferred embodiment of the polymer used in layer C is the same as the preferred embodiment of the polymer used in layer A having a dielectric tangent of 0.01 or less.
• the polymer contained in layer C may be the same as or different from the polymer contained in layer A or layer B, but from the viewpoint of adhesion between layer A and layer C, it is preferable that the polymer is the same as the polymer contained in layer A.
• layer C contains an epoxy resin to bond the metal layer to layer A.
• the epoxy resin is preferably a crosslinked product of a multifunctional epoxy compound.
• a multifunctional epoxy compound is a compound having two or more epoxy groups.
• the number of epoxy groups in a multifunctional epoxy compound is preferably 2 to 4.
• layer C contains an aromatic polyester amide and an epoxy resin.
• the layer C may contain a filler.
• the preferred embodiments of the filler used in Layer C are the same as those of the filler used in Layer A.
• Layer C may contain additives other than those mentioned above. Preferred embodiments of the other additives used in Layer C are the same as those of the other additives used in Layer A, except as described below.
• the average thickness of layer C is preferably thinner than the average thickness of layer A from the viewpoints of the dielectric tangent of the laminate and adhesion to metals.
• T A /T C which is the ratio of the average thickness T A of Layer A to the average thickness T C of Layer C, is preferably greater than 1, more preferably from 2 to 100, even more preferably from 2.5 to 20, and particularly preferably from 3 to 10, from the viewpoints of the dielectric tangent of the laminate and the adhesion to the metal layer.
• T B /T C which is the ratio of the average thickness T B of Layer B to the average thickness T C of Layer C, is preferably greater than 1, more preferably from 2 to 100, even more preferably from 2.5 to 20, and particularly preferably from 3 to 10, from the viewpoints of the dielectric tangent of the laminate and the adhesion to the metal layer.
• the average thickness of layer C is preferably 0.1 ⁇ m to 20 ⁇ m, more preferably 0.5 ⁇ m to 15 ⁇ m, even more preferably 1 ⁇ m to 10 ⁇ m, and particularly preferably 2 ⁇ m to 8 ⁇ m.
• the average thickness of the laminate according to the present disclosure is preferably 6 ⁇ m to 200 ⁇ m, more preferably 12 ⁇ m to 100 ⁇ m, and particularly preferably 20 ⁇ m to 80 ⁇ m, from the viewpoints of strength and electrical properties (characteristic impedance) when laminated with a metal layer.
• the average thickness of the laminate is measured at any five points using an adhesive thickness gauge, such as an electronic micrometer (product name "KG3001A", manufactured by Anritsu Corporation), and the average value is calculated.
• an adhesive thickness gauge such as an electronic micrometer (product name "KG3001A”, manufactured by Anritsu Corporation)
• the laminate according to the present disclosure preferably has a dielectric loss tangent of 0.01 or less, more preferably 0.006 or less, and even more preferably greater than 0 and 0.004 or less.
• Method for producing the laminate according to the present disclosure is not particularly limited, and known methods can be referred to.
• Suitable film-forming methods include, for example, co-casting, multi-layer coating, and co-extrusion. Among these, the co-casting method is preferred.
• the multilayer structure of the laminate is produced by the co-casting method or the multi-layer coating method
• Solvents include, for example, halogenated hydrocarbons such as dichloromethane, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, 1-chlorobutane, chlorobenzene, and o-dichlorobenzene; halogenated phenols such as p-chlorophenol, pentachlorophenol, and pentafluorophenol; ethers such as diethyl ether, tetrahydrofuran, and 1,4-dioxane; ketones such as acetone and cyclohexanone; esters such as ethyl acetate and ⁇ -butyrolactone; and ethylene carbonate.
• halogenated hydrocarbons such as dichloromethane, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, 1-
• organic solvent examples include carbonates such as propylene carbonate and propylene carbonate; amines such as triethylamine; nitrogen-containing heterocyclic aromatic compounds such as pyridine; nitriles such as acetonitrile and succinonitrile; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone, and urea compounds such as tetramethylurea; nitro compounds such as nitromethane and nitrobenzene; sulfur compounds such as dimethyl sulfoxide and sulfolane; and phosphorus compounds such as hexamethylphosphoramide and tri-n-butylphosphoric acid, and two or more of these may be used.
• carbonates such as propylene carbonate and propylene carbonate
• amines such as triethylamine
• nitrogen-containing heterocyclic aromatic compounds such as pyridine
• nitriles such as acetonitrile and succinon
• the solvent is preferably a solvent mainly composed of an aprotic compound, particularly an aprotic compound without halogen atoms, because it is less corrosive and easier to handle, and the ratio of the aprotic compound to the entire solvent is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass.
• amides such as N,N-dimethylformamide, N,N-dimethylacetamide, tetramethylurea, and N-methylpyrrolidone, or esters such as ⁇ -butyrolactone, because they easily dissolve liquid crystal polymers, and N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone are more preferable.
• a solvent mainly composed of a compound having a dipole moment of 3 to 5 is preferred because it easily dissolves the liquid crystal polymer, and the proportion of the compound having a dipole moment of 3 to 5 in the entire solvent is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass.
• the aprotic compound it is preferable to use a compound having a dipole moment of 3 to 5.
• the solvent is preferably a solvent mainly composed of a compound having a boiling point of 220° C. or lower at 1 atmospheric pressure, because it is easy to remove.
• the proportion of the compound having a boiling point of 220° C. or lower at 1 atmospheric pressure in the entire solvent is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass.
• the aprotic compound it is preferable to use a compound having a boiling point of 220° C. or lower at 1 atmospheric pressure.
• a support may be used when the laminate is produced by the above-mentioned co-casting method, multi-layer coating method, co-extrusion method, or the like.
• the support include a metal drum, a metal band, a glass plate, a resin film, and a metal foil.
• the support is preferably a metal drum, a metal band, or a resin film.
• resin films include polyimide (PI) films, and examples of commercially available products include U-PIREX S and U-PIREX R manufactured by Ube Industries, Ltd., Kapton manufactured by DuPont-Toray Co., Ltd., and IF30, IF70, and LV300 manufactured by SKC Kolon PI.
• the support may have a surface treatment layer formed on its surface so that it can be easily peeled off.
• the surface treatment layer may be made of hard chrome plating, fluororesin, or the like.
• the average thickness of the support is not particularly limited, but is preferably from 25 to 75 ⁇ m, and more preferably from 50 to 75 ⁇ m.
• the method for removing at least a portion of the solvent from the cast or applied film-like composition (coating film) is not particularly limited, and any known drying method can be used.
• the laminate according to the present disclosure can be appropriately combined with stretching in terms of controlling molecular orientation and adjusting the thermal expansion coefficient and mechanical properties.
• the stretching method is not particularly limited, and known methods can be referred to. It may be performed in a state containing a solvent or in a dry film state. Stretching in a state containing a solvent may be performed by gripping the laminate and stretching it, or it may be performed by utilizing autogenous shrinkage due to drying without stretching it. Stretching is particularly effective for the purpose of improving the breaking elongation and breaking strength when the film brittleness is reduced by the addition of inorganic fillers, etc.
• the laminate according to the present disclosure can be used for various applications, and among others, can be suitably used as a film for electronic components such as printed wiring boards, and can be even more suitably used as a flexible printed circuit board. Moreover, the laminate according to the present disclosure can be suitably used as a liquid crystal polymer film for metal bonding.
• the wiring board according to the present disclosure comprises a substrate, a wiring pattern disposed on at least one surface of the substrate, a layer B disposed between the wiring patterns and on the wiring patterns, and a layer A disposed on layer B, wherein layer B contains a silsesquioxane polymer and has a dielectric loss tangent of 0.01 or less.
• the wiring board according to the present disclosure includes a substrate, a wiring pattern arranged on at least one surface of the substrate, a layer B arranged between the wiring patterns and on the wiring pattern, and a layer A arranged on layer B, and layer B may be a polymer film according to the present disclosure.
• the wiring board according to the present disclosure contains a silsesquioxane polymer, which reduces gaps around the wiring pattern and has excellent heat resistance.
• the material of the substrate is not particularly limited, but preferably contains a resin, more preferably contains a liquid crystal polymer, and is more preferably a liquid crystal polymer film.
• the average thickness of the substrate is not particularly limited, but is preferably 5 ⁇ m to 100 ⁇ m, more preferably 10 ⁇ m to 80 ⁇ m, and even more preferably 20 ⁇ m to 70 ⁇ m.
• the wiring board according to the present disclosure has a wiring pattern on at least one surface of the substrate. Since layer B is disposed between and on the wiring patterns, the wiring pattern is embedded in the wiring board according to the present disclosure.
• the wiring pattern can be embedded in the wiring board, for example, by the following method. First, a metal layer is formed on the substrate, and the metal layer is etched in a pattern. This results in a substrate with a wiring pattern. Next, the substrate with a wiring pattern and another substrate having layers A and B are layered together such that the wiring pattern in the substrate with a wiring pattern and layer B are in contact with each other. After the substrate with a wiring pattern and the other substrate are layered together, they may be bonded together or heat fused together. This results in a wiring board with an embedded wiring pattern.
• the material of the wiring pattern is not particularly limited, but it is preferably a metal, and more preferably silver or copper.
• the thickness of the wiring pattern is not particularly limited, but is preferably 5 ⁇ m to 40 ⁇ m, and more preferably 5 ⁇ m to 35 ⁇ m.
• the thickness of the wiring pattern is measured by cutting the wiring board with a microtome and observing it with an optical microscope.
• the wiring board according to the present disclosure has a layer B between the wiring patterns and on the wiring patterns.
• the layer B contains a silsesquioxane polymer.
• the silsesquioxane polymer contained in layer B in the wiring board according to the present disclosure is preferably a silsesquioxane polymer used as a raw material that has been thermally cured.
• layer B preferably contains a silsesquioxane polymer having a crosslinked structure in which the molecules are crosslinked.
• the silsesquioxane polymer preferably contains at least one selected from the group consisting of a partial structure represented by the following formula (T1a), a partial structure represented by the following formula (T2a), and a partial structure represented by the following formula (T3a): R 2 -Si(-OX) 2 O 1/2 ... (T1a) R 2 -Si(-OX)O 2/2 ... (T2a) R 2 -SiO 3/2 ... (T3a)
• R2 each independently represents an organic group, and each R2 may be linked to another.
• X represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• examples of R2 include the same as R1 in the above formulae (T1) to (T3).
• R2 When R2 are linked to each other, R2 preferably includes a structure derived from at least one crosslinkable group selected from the group consisting of a vinyl group, an allyl group, a styryl group, and a maleimide group.
• the structure derived from a crosslinkable group means a structure obtained by polymerization of the crosslinkable group.
• the silsesquioxane polymer contains a partial structure represented by formula (T2a) and a partial structure represented by formula (T3a), and the molar ratio of the partial structure represented by formula (T3a) to the partial structure represented by formula (T2a) is preferably 50 or more, and more preferably 70 or more. There is no particular upper limit to the above molar ratio.
• the molar ratio of the partial structure represented by formula (T3a) to the partial structure represented by formula (T2a) is calculated from the peak area ratio of 29 Si-NMR.
• the content of the silsesquioxane polymer is preferably 50% by mass to 100% by mass, and more preferably 60% by mass to 90% by mass, based on the total mass of Layer B.
• Layer B further contains a thermoplastic resin or a thermosetting resin other than the silsesquioxane polymer.
• the preferred aspects of the thermoplastic resin and thermosetting resin that may be contained in Layer B in the wiring board according to the present disclosure are the same as the preferred aspects of the thermoplastic resin and thermosetting resin that may be contained in the polymer film according to the present disclosure.
• layer B contains a filler.
• Preferred embodiments of the filler that may be contained in layer B are the same as the preferred embodiments of the filler that may be contained in layer B of the laminate according to the present disclosure.
• Layer B may contain additives other than those mentioned above. Preferred embodiments of other additives that may be contained in Layer B are the same as preferred embodiments of other additives that may be contained in the polymer film according to the present disclosure.
• the thickness of the thickest part of Layer B is preferably 10 ⁇ m or more, more preferably 15 ⁇ m to 40 ⁇ m, and even more preferably 20 ⁇ m to 30 ⁇ m.
• the thickest part here refers to the part where the wiring pattern is not embedded.
• the wiring board according to the present disclosure has a layer A on which a layer B is provided.
• a preferred embodiment of the layer A is the same as the preferred embodiment of the layer A included in the laminate according to the present disclosure.
• the wiring board according to the present disclosure preferably further includes layer C in addition to layer A and layer B, and layer C is preferably disposed on layer A.
• a preferred embodiment of layer C is the same as a preferred embodiment of layer C that may be included in the laminate according to the present disclosure.
• a first aspect of the method for producing a wiring board according to the present disclosure preferably includes the steps of: superposing the laminate according to the present disclosure on a wiring pattern of a substrate having a wiring pattern; and heating the substrate having a wiring pattern and the laminate according to the present disclosure in a superposed state to obtain a wiring board.
• the substrate having a wiring pattern and the laminate are superposed such that the wiring pattern of the substrate having a wiring pattern contacts layer B of the laminate.
• the laminate according to the present disclosure is superimposed on the wiring pattern of a substrate having a wiring pattern.
• the laminate When stacking the laminates, the laminate may simply be placed on the wiring pattern, or the laminate may be pressed onto the wiring pattern by applying pressure.
• the substrate with a wiring pattern may have the wiring pattern formed on only one side of the substrate, or may have the wiring pattern formed on both sides of the substrate.
• the substrate with a wiring pattern can be produced using a known method. For example, a metal layer is attached to at least one surface of the substrate to obtain a wiring board comprising the substrate and a metal layer disposed on at least one surface of the substrate. The metal layer is subjected to a known patterning process to obtain the substrate with a wiring pattern.
• the preferred aspects of the substrate and wiring pattern in the substrate with a wiring pattern are the same as those described above in the section on wiring boards.
• the heating method is not particularly limited, and can be performed using a heat press, for example.
• the heating temperature is preferably 50°C to 300°C, and more preferably 100°C to 250°C.
• the pressure is preferably 0.5 MPa to 30 MPa, and more preferably 1 MPa to 20 MPa.
• the heating time is not particularly limited and may be, for example, 1 minute to 2 hours.
• a second aspect of the method for producing a wiring board according to the present disclosure preferably includes the steps of applying a layer A-forming solution onto a support to form layer A, superposing a polymer film according to the present disclosure and a substrate with a wiring pattern on layer A in this order, and heating the support on which layer A has been formed, the polymer film according to the present disclosure, and the substrate with a wiring pattern in a superposed state to obtain a wiring board.
• the polymer film and the substrate with a wiring pattern are superposed so that the wiring pattern of the substrate with a wiring pattern is in contact with the polymer film.
• the support may be the same as the support used in the manufacturing method of the laminate described above.
• the details of the substrate with wiring pattern are the same as those of the first embodiment described above.
• the wiring board according to the present disclosure can be used for various applications, and among them, the wiring board according to the present disclosure can be suitably used as a flexible printed circuit board.
• silsesquioxane polymer Preferred embodiments of the silsesquioxane polymer according to the present disclosure are the same as the preferred embodiments of the silsesquioxane polymer contained in the polymer film according to the present disclosure.
• the silsesquioxane polymer according to the present disclosure has a dielectric tangent of 0.01 or less, preferably 0.006 or less, more preferably 0.005 or less, even more preferably 0.003 or less, and particularly preferably 0.0025 or less.
• the dielectric tangent of the silsesquioxane polymer according to the present disclosure is preferably greater than 0 and less than 0.01.
• the polymer composition according to the present disclosure comprises a silsesquioxane polymer according to the present disclosure.
• a preferred embodiment of the silsesquioxane polymer contained in the polymer composition according to the present disclosure is the same as a preferred embodiment of the silsesquioxane polymer contained in the polymer film according to the present disclosure.
• the polymer composition according to the present disclosure preferably further comprises a thermoplastic or thermosetting resin other than the silsesquioxane polymer.
• a thermoplastic or thermosetting resin other than the silsesquioxane polymer.
• Preferred aspects of the thermoplastic resin or thermosetting resin that may be contained in the polymer composition according to the present disclosure are the same as preferred aspects of the thermoplastic resin or thermosetting resin that may be contained in the polymer film according to the present disclosure.
• the polymer composition according to the present disclosure preferably further comprises an inorganic filler.
• Preferred embodiments of the inorganic filler that may be contained in the polymer composition according to the present disclosure are the same as preferred embodiments of the inorganic filler that may be contained in the polymer film according to the present disclosure.
• the aromatic polyesteramide A1a was heated from room temperature to 160°C over 2 hours and 20 minutes in a nitrogen atmosphere, then heated from 160°C to 180°C over 3 hours and 20 minutes, and held at 180°C for 5 hours to carry out solid-state polymerization, and then cooled.
• the aromatic polyesteramide A1b was then pulverized in a pulverizer to obtain a powdered aromatic polyesteramide A1b.
• the flow-initiation temperature of the aromatic polyesteramide A1b was 220°C.
• the aromatic polyester amide A1b was heated in a nitrogen atmosphere from room temperature to 180°C over 1 hour 25 minutes, then heated from 180°C to 255°C over 6 hours 40 minutes, and held at 255°C for 5 hours to carry out solid-state polymerization, and then cooled to obtain a powdered aromatic polyester amide P1.
• the flow initiation temperature of the aromatic polyesteramide P1 was 302° C.
• the melting point of the aromatic polyesteramide P1 was measured using a differential scanning calorimeter and found to be 311° C.
• the dielectric tangent of the aromatic polyesteramide P1 was 0.003.
• the solubility of the aromatic polyesteramide P1 in N-methylpyrrolidone at 140° C. was 1% by mass or more.
• PP-1 Liquid crystal polymer particles prepared according to the following production method
• PP-2 Liquid crystal polymer particles prepared according to the following production method
• acetic anhydride (1.08 molar equivalent relative to the hydroxyl group) was further added. Under a nitrogen gas stream, the temperature was raised from room temperature to 150°C over 15 minutes while stirring, and refluxed at 150°C for 2 hours. Next, while distilling off the by-produced acetic acid and unreacted acetic anhydride, the temperature was raised from 150°C to 310°C over 5 hours, and the polymer was taken out and cooled to room temperature. The obtained polymer was heated from room temperature to 295°C over 14 hours, and solid-phase polymerized at 295°C for 1 hour.
• the liquid crystal polymer particles PP-1 had a median diameter (D50) of 7 ⁇ m, a dielectric dissipation factor of 0.0007, and a melting point of 334°C.
• the liquid crystal polymer particles PP-2 had a median diameter (D50) of 10 ⁇ m, a dielectric tangent of 0.0021, and a melting point of 325 ° C.
• Silsesquioxane polymers SQ2 to SQ8 were synthesized by changing the methyltrimethoxysilane used in the synthesis of silsesquioxane polymer SQ1 to the following raw materials.
• Silsesquioxane polymers SQ9 to SQ16 were synthesized by changing 0.3 mol of methyltrimethoxysilane used in the synthesis of silsesquioxane polymer SQ1 to the following two raw materials, and adjusting the amounts used to the following amounts.
• ⁇ SQ2 raw material phenyltrimethoxysilane ⁇ SQ3 raw material: vinyltrimethoxysilane ⁇ SQ4 raw material: allyltrimethoxysilane ⁇ SQ5 raw material: styryltrimethoxysilane ⁇ SQ6 raw material: N-[3-(trimethoxysilyl)propyl]maleimide ⁇ SQ7 raw material: [2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane ⁇ SQ8 raw material: 3-(trimethoxysilyl)propyl methacrylate ⁇ SQ9 raw material: styryltrimethoxysilane (0.15 mol) / decyltrimethoxysilane (0.15 mol) Raw material for SQ10: styryltrimethoxysilane (0.075 mol) / decyltrimethoxysilane (0.225 mol) Raw material for
• Each of the silsesquioxane polymers SQ1 to SQ8 contained a partial structure represented by formula (T2) and a partial structure represented by the following formula (T3).
• SQ1 In formula (T2) and formula (T3), R 1 is a methyl group.
• SQ2 In formula (T2) and formula (T3), R 1 is a phenyl group.
• SQ3 In formula (T2) and formula (T3), R 1 is a vinyl group.
• SQ4 In formula (T2) and formula (T3), R 1 is an allyl group.
• SQ5 In formula (T2) and formula (T3), R 1 is a styryl group.
• SQ6 In formula (T2) and formula (T3), R 1 is a 3-maleimidopropyl group.
• R 1 is a 2-(3,4-epoxycyclohexyl)ethyl group.
• silsesquioxane polymers SQ9 to SQ16 contained partial structures represented by formulae (T2k) and (2m), as well as partial structures represented by the following formulae (T3k) and (T3m).
• R 11 —Si(—OX)O 2/2 ...(T2k)
• R 12 —Si(—OX)O 2/2 ...(T2m)
• T3m) All of the silsesquioxane polymers SQ9 to SQ16 contained partial structures represented by formulae (T2k) and (2m), as well as partial structures represented by the following formulae (T3k) and (T3m).
• SQ9 In formulae (T2k) and (T3k), R 11 is a styryl group, and in formulae (T2m) and (T3m), R 12 is a decyl group.
• SQ10 In (T2k) and formula (T3k), R 11 is a styryl group, and in (T2m) and formula (T3m), R 12 is a decyl group.
• SQ11 In (T2k) and formula (T3k), R 11 is a styryl group, and in (T2m) and formula (T3m), R 12 is a hexyl group.
• SQ12 In (T2k) and formula (T3k), R 11 is a vinyl group, and in (T2m) and formula (T3m), R 12 is a decyl group.
• SQ13 In (T2k) and formula (T3k), R 11 is a phenyl group, and in (T2m) and formula (T3m), R 12 is a hexyl group.
• SQ14 In (T2k) and formula (T3k), R 11 is a phenyl group, and in (T2m) and formula (T3m), R 12 is an octyl group.
• SQ15 In (T2k) and formula (T3k), R 11 is a phenyl group, and in (T2m) and formula (T3m), R 12 is a hexyl group.
• SQ16 In (T2k) and formula (T3k), R 11 is a phenyl group, and in (T2m) and formula (T3m), R 12 is an octyl group.
• T1 Bismaleimide resin, product name "MIR-3000", manufactured by Nippon Kayaku Co., Ltd.
• F1 Silica particles, product name "SC2500-SPJ”, manufactured by Admatechs Co., Ltd.
• F2 Polytetrafluoroethylene (PTFE) resin particles, product name "TF-9205", manufactured by 3M Co., Ltd.
• PTFE Polytetrafluoroethylene
• the solution for forming layer C was applied to the treated surface of a copper foil (manufactured by Fukuda Metal Foil and Powder Co., Ltd., CF-T4X-SV-18, thickness 18 ⁇ m, surface roughness of the attachment surface (treated surface) Rz 0.85 ⁇ m) using an applicator, and dried by blowing air at 150 ° C. for 1 hour.
• the film thickness of layer C after drying was 3 ⁇ m.
• the solution for forming layer A was applied to the obtained layer C using an applicator, and dried by blowing air at 50 ° C. for 3 hours. Thereafter, annealing treatment was performed at 300 ° C. for 3 hours under a nitrogen atmosphere.
• the film thickness of layer A was as shown in Table 1.
• the solution for forming layer B was applied to the obtained layer A using an applicator, and dried by blowing air at 90 ° C. for 2 hours, to obtain a laminate (single-sided copper-clad multilayer film) having a copper layer, layer C, layer A, and layer B in this order.
• the layer B forming solution was applied onto a polytetrafluoroethylene sheet using an applicator, and dried with air at 90° C. for 2 hours. Thereafter, the layer B was peeled off from the polytetrafluoroethylene sheet to obtain a bonding sheet.
• thermocompression bonding machine product name "MP-SNL", manufactured by Toyo Seiki Seisakusho Co., Ltd.
• MP-SNL manufactured by Toyo Seiki Seisakusho Co., Ltd.
• the copper foils on both sides of the double-sided copper-clad laminate were etched and patterned to produce a substrate with a wiring pattern including a ground line and three pairs of signal lines on both sides of the substrate.
• the length of the signal lines was 50 mm, and the width was set so that the characteristic impedance was 50 ⁇ .
• the above-mentioned substrate having a wiring pattern was laminated on the layer B side of the obtained single-sided copper-clad multilayer film, and hot pressed at 160° C. and 4 MPa for 1 hour to obtain a wiring board.
• the obtained wiring board had a wiring pattern (ground line and signal line) embedded therein, and the thickness of the wiring pattern was 18 ⁇ m.
• wiring boards were produced using the above bonding sheets.
• the obtained solution for forming layer C was applied to the treated surface of a copper foil (manufactured by Fukuda Metal Foil and Powder Co., Ltd., CF-T4X-SV-18, thickness 18 ⁇ m, surface roughness of the attachment surface (treated surface) Rz 0.85 ⁇ m) using an applicator, and dried by blowing air at 150° C. for 1 hour.
• the film thickness of layer C after drying was 3 ⁇ m.
• the solution for forming layer A was applied to the obtained layer C using an applicator, and dried by blowing air at 50° C. for 3 hours. Thereafter, annealing treatment was performed at 300° C.
• the film thickness of layer A was as shown in Table 1.
• the above-mentioned bonding sheet was placed on the obtained layer A, and the above-mentioned substrate with a wiring pattern was further superimposed on the bonding sheet, and a wiring board was obtained by performing a heat press for 1 hour under conditions of 160° C. and 4 MPa.
• the wiring board had a wiring pattern (ground line and signal line) embedded therein, and the thickness of the wiring pattern was 18 ⁇ m.
• the elastic modulus of layer B of the single-sided copper-clad multilayer film was measured as the indentation elastic modulus using a nanoindentation method.
• the indentation elastic modulus was measured using a microhardness tester (product name "DUH-W201", manufactured by Shimadzu Corporation) at 160°C, by applying a load at a loading rate of 0.28 mN/s with a Vickers indenter, holding the maximum load of 10 mN for 10 seconds, and then unloading at a loading rate of 0.28 mN/s.
• the storage modulus A of layer B of the single-sided copper-clad multilayer film or the bonding sheet was evaluated at 25° C. to 40° C. Specifically, it was determined whether the storage modulus A was within a specific numerical range at any temperature between 25° C. and 40° C.
• the evaluation criteria were as follows: A: The storage modulus A is 5 ⁇ 10 6 Pa to 5 ⁇ 10 7 Pa at any temperature from 25° C. to 40° C. B: The storage modulus A is 10 6 Pa to 10 8 Pa at any temperature between 25° C. and 40° C., and does not fall under the category of A. C: The storage modulus A is 10 4 Pa to 10 8 Pa at any temperature between 25° C. and 40° C., and does not fall under evaluations A and B. D: Does not fall under any of the above ratings A to C.
• the storage modulus B of layer B of the single-sided copper-clad multilayer film or the bonding sheet was evaluated at 150° C. to 250° C. Specifically, it was determined whether the storage modulus B fell within a specific numerical range at any temperature between 150° C. and 250° C.
• the evaluation criteria were as follows: A: The storage modulus B is 10 5 Pa or less at any temperature between 150°C and 250°C. B: The storage modulus B is 3 ⁇ 10 5 Pa or less at any temperature between 150° C. and 250° C., and does not correspond to evaluation A.
• C The storage modulus B is 10 6 Pa or less at any temperature between 150° C. and 250° C., and does not fall under evaluations A and B.
• D Does not fall under any of the above ratings A to C.
• Storage modulus C at 25°C to 40°C The storage modulus C of the silsesquioxane polymer was evaluated at 25° C. to 40° C. Specifically, it was determined whether the storage modulus C fell within a specific numerical range at any temperature between 25° C. and 40° C. The evaluation criteria were the same as those for the storage modulus A.
• Storage modulus D at 150°C to 250°C The storage modulus D of the silsesquioxane polymer was evaluated at 150° C. to 250° C. Specifically, it was determined whether the storage modulus D fell within a specific numerical range at any temperature between 150° C. and 250° C. The evaluation criteria were the same as those for the storage modulus B.
• the dielectric loss tangent of the single-sided copper-clad laminate film and the wiring board was measured using the film obtained by removing the copper foil from the copper-clad laminate with an aqueous solution of ferric chloride, washing with pure water, and drying. For the bonding sheet, the measurement was performed using the bonding sheet as it was.
• the dielectric loss tangent was measured at a frequency of 28 GHz by a resonance perturbation method.
• a 28 GHz cavity resonator (Kanto Electronics Application Development Co., Ltd.'s "CP531") was connected to a network analyzer (Agilent Technology's "E8363B”), and the measurement sample was inserted into the cavity resonator.
• the dielectric loss tangent of the measurement sample was measured from the change in resonance frequency before and after insertion for 96 hours under an environment of 25°C temperature and 60% RH.
• Heat resistance A Solder immersion test
• the wiring board was cut into a size of 30 mm x 30 mm to prepare an evaluation sample.
• the evaluation sample was immersed in hot solder at 288°C for 10 seconds three times. After immersion, the evaluation sample was cut with a razor, and the cross section was observed under an optical microscope to evaluate the peeling state based on the following evaluation criteria.
• C Peeling was observed with a width of more than 1 mm.
• SQ means silsesquioxane polymer.
• T3/T2 means the molar ratio of the partial structure represented by formula (T3) to the partial structure represented by formula (T2) in the silsesquioxane polymer contained in layer B of the single-sided copper-clad multilayer film or in the bonding sheet.
• T3a/T2a means the molar ratio of the partial structure represented by formula (T3a) to the partial structure represented by formula (T2a) in the silsesquioxane polymer contained in layer B of the wiring board.
• the laminate includes a layer A and a layer B disposed on at least one surface of the layer A, and the layer B includes a silsesquioxane polymer and has a dielectric loss tangent of 0.01 or less, and therefore has excellent step conformability and heat resistance.
• the polymer film contains a silsesquioxane polymer and has a dielectric loss tangent of 0.01 or less, and therefore has excellent step conformability and heat resistance.

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• 2023
  • 2023-10-20 JP JP2024562614A patent/JPWO2024122205A1/ja active Pending
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