WO2023149394A1 - 重合体、組成物、硬化物、積層体および電子部品 - Google Patents

重合体、組成物、硬化物、積層体および電子部品 Download PDF

Info

Publication number
WO2023149394A1
WO2023149394A1 PCT/JP2023/002850 JP2023002850W WO2023149394A1 WO 2023149394 A1 WO2023149394 A1 WO 2023149394A1 JP 2023002850 W JP2023002850 W JP 2023002850W WO 2023149394 A1 WO2023149394 A1 WO 2023149394A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
polymer
substituted
compound
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2023/002850
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
敏明 門田
俊介 飯塚
浩一 岡本
健太 西野
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JSR Corp
Original Assignee
JSR Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JSR Corp filed Critical JSR Corp
Priority to JP2023578543A priority Critical patent/JPWO2023149394A1/ja
Priority to EP23749710.2A priority patent/EP4474427A4/en
Priority to KR1020247020563A priority patent/KR20240136937A/ko
Priority to CN202380015052.3A priority patent/CN118401610A/zh
Priority to US18/834,042 priority patent/US20250122404A1/en
Publication of WO2023149394A1 publication Critical patent/WO2023149394A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • 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
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/02—Polyamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/024—Polyamines containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0273—Polyamines containing heterocyclic moieties in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/0644—Poly(1,3,5)triazines
    • 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
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences

Definitions

  • One embodiment of the present invention relates to a polymer, composition, cured product, laminate or electronic component.
  • Multilayer printed wiring boards made by laminating resin films have weaknesses in mechanical strength, heat resistance, flame retardancy, and thermal conductivity compared to prepregs manufactured using glass cloth or the like. is known, and in recent years, techniques for improving this weak point have been reported (see, for example, Patent Documents 1 to 3).
  • each electronic component material may be required to be bonded using a polymer (composition containing).
  • a polymer or a composition containing a polymer It is also required to be able to uniformly apply a substance to a substrate (excellent coatability) and to have high adhesion to the substrate of a layer obtained from the polymer or a composition containing the polymer.
  • One embodiment of the present invention provides a polymer having excellent heat resistance, being soluble in a general-purpose solvent, and having excellent coatability and adhesion to a substrate.
  • a composition capable of forming a cured product (cured product layer) with excellent adhesion is provided.
  • a configuration example of the present invention is as follows.
  • -N(R')-R 3 -N(R')- is a structure derived from unsubstituted or substituted dimer diamine
  • R', R 1 and R 2 is each independently a hydrogen atom, a halogen atom, an unsubstituted or substituted hydrocarbon group of 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic aliphatic of 3 to 20 carbon atoms or a heterocyclic aromatic group having 3 to 20 carbon atoms which is unsubstituted or substituted
  • —NR 1 R 2 is the number of ring-constituting atoms in which R 1 and R 2 are bonded to each other It may be 5 to 20 nitrogen-containing heterocyclic groups.
  • R′, R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted A heterocyclic aliphatic group having 3 to 20 carbon atoms substituted by or an unsubstituted or substituted heterocyclic aromatic group having 3 to 20 carbon atoms, and R 4 has 6 carbon atoms -30 divalent aromatic hydrocarbon group, C5-20 divalent alicyclic hydrocarbon group, C1-20 divalent chain hydrocarbon group, -( R41 -O) a divalent group represented by m- , a divalent silicon-containing group, a group in which two or more selected from these groups are combined, at least part of these groups are oxygen atoms, nitrogen atoms and sulfur A group substituted with at least one selected from atoms, or a group partially substituted with a substituent, R 41 is independently an alkylene having 2 to 4 carbon atoms,
  • the curable compound (C) includes epoxy compounds, cyanate ester compounds, vinyl compounds, silicone compounds, oxazine compounds, maleimide compounds, allyl compounds, oxetane compounds, methylol compounds, (meth)acrylic compounds, oxazoline compounds and propargyl.
  • [7] A cured product obtained by curing the composition according to any one of [1] to [6].
  • [8] A laminate comprising a substrate and a cured product layer formed using the composition according to any one of [1] to [6].
  • [9] An electronic component having the laminate according to [8].
  • -N(R')-R 3 -N(R')- is a structure derived from unsubstituted or substituted dimer diamine, and R', R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted group having 3 to 20 carbon atoms.
  • R 4 is a divalent aromatic hydrocarbon having 6 to 30 carbon atoms a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, a chain divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent group represented by —(R 41 —O) m — , a divalent silicon-containing group, a group in which two or more selected from these groups are combined, at least a portion of these groups are substituted with at least one selected from an oxygen atom, a nitrogen atom and a sulfur atom or a group partially substituted by a substituent, R 41 is independently an alkylene having 2 to 4 carbon atoms, m is an integer of 1 to 70, and —NR 1 R 2 may be a nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which R 1 and R 2 are bonded to each other, and -
  • [11] A molded article obtained by molding the polymer according to [10].
  • [12] A laminate having a substrate and a layer formed using the polymer of [10].
  • [13] An electronic component comprising the laminate according to [12].
  • -N(R')-R 3 -N(R')- is a structure derived from unsubstituted or substituted dimer diamine, and R', R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted group having 3 to 20 carbon atoms.
  • R 4 is a divalent aromatic hydrocarbon having 6 to 30 carbon atoms a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, a chain divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent group represented by —(R 41 —O) m — , a divalent silicon-containing group, a group in which two or more selected from these groups are combined, at least a portion of these groups are substituted with at least one selected from an oxygen atom, a nitrogen atom and a sulfur atom or a group partially substituted by a substituent, R 41 is independently an alkylene having 2 to 4 carbon atoms, m is an integer of 1 to 70, and —NR 1 R 2 may be a nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which R 1 and R 2 are bonded to each other, and -
  • a polymer that is excellent in heat resistance, soluble in general-purpose solvents, and excellent in coatability and adhesion to substrates such as copper substrates and gold substrates.
  • a composition capable of forming a cured product (cured product layer) having excellent heat resistance and excellent applicability and adhesion to substrates such as copper substrates and gold substrates. can do.
  • FIG. 1 is a 1 H-NMR spectrum of the polymer obtained in Example 2.
  • FIG. 2 is the 1 H-NMR spectrum of the polymer obtained in Example 5.
  • FIG. 3 is the 1 H-NMR spectrum of the polymer obtained in Example 6.
  • FIG. 4 is the 1 H-NMR spectrum of the polymer obtained in Example 8.
  • FIG. 5 is the 1 H-NMR spectrum of the polymer obtained in Example 9.
  • FIG. 6 is the 1 H-NMR spectrum of the polymer obtained in Example 10.
  • compositions according to one embodiment of the present invention are a polymer having a repeating unit represented by the following formula (1) (hereinafter referred to as “polymer (1 )”).
  • the polymer (1) contained in the present composition may be of one type or two or more types.
  • a polymer according to one embodiment of the present invention (hereinafter also referred to as “polymer (2)”) includes a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2) contains
  • the polymer (2) may have structural units other than the repeating unit represented by formula (1) and the repeating unit represented by formula (2) below.
  • a polymer according to one embodiment of the present invention (hereinafter also referred to as "polymer (3)”) has a phenolic hydroxyl group, an allyl group, a vinyl group, a phenolic hydroxyl group, an allyl group, a vinyl group, (Meth)acryloyl group, maleimide group, propargyl group, ethynyl group, aromatic hydrocarbon group, aliphatic hydrocarbon group, or at least one group selected from heterocyclic groups (hereinafter also referred to as "terminal group”). ).
  • the polymer (3) may have a repeating unit represented by the formula (1), a repeating unit represented by the following formula (2), and structural units other than the terminal group.
  • the term “end” refers to at least one end of the main chain (longest chain) of the polymer. do not have.
  • the polymers (1) to (3) are also collectively referred to as "this polymer”.
  • a repeating unit represented by the following formula (1) is bonded to, for example, another structural unit or a terminal structure described below.
  • a raw material constituting a repeating unit represented by the following formula (1) e.g., a compound represented by the following formula (A) or (B)
  • a repeating unit represented by the following formula (2) is bonded to, for example, a repeating unit represented by the following formula (1) or a terminal structure.
  • a raw material constituting a repeating unit represented by the following formula (2) e.g., a compound represented by the following formula (A) or (C)
  • the following end blocking agent derived structure preferably the terminal group.
  • This polymer is a polymer having a repeating unit represented by the following formula (1).
  • the present polymer has a repeating unit represented by the following formula (1), it is possible to obtain a polymer with excellent solubility in solvents, and it is possible to improve the applicability to substrates. is.
  • Two or more kinds of the present polymer can be used for the purpose of adjusting the solubility in the solvents described below, the solubility with other components, and various physical properties of the composition.
  • -N(R')-R 3 -N(R')- is a structure derived from unsubstituted or substituted dimer diamine
  • R', R 1 and R 2 is each independently a hydrogen atom, a halogen atom, an unsubstituted or substituted hydrocarbon group of 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic aliphatic of 3 to 20 carbon atoms or a heterocyclic aromatic group having 3 to 20 carbon atoms which is unsubstituted or substituted
  • —NR 1 R 2 is the number of ring-constituting atoms in which R 1 and R 2 are bonded to each other It may be 5 to 20 nitrogen-containing heterocyclic groups.
  • Structures derived from unsubstituted or substituted dimer diamine include, for example, a divalent dimeric diamine residue derived from a dimer acid diamine or at least A group partially substituted with a substituent can be mentioned.
  • the dimer acid-type diamine is a dimer acid (cyclic and acyclic dimer acid (mainly composed of 36 carbon atoms) obtained as a dimer of unsaturated fatty acid (18 carbon atoms)).
  • the dimer acid-type diamine is a compound derived from a dimer acid, which is a dimer of an unsaturated fatty acid such as oleic acid (see JP-A-9-12712, etc.), and various known dimer diamines can be used without particular limitation. Available.
  • Dimer acid is a known dibasic acid obtained by an intermolecular polymerization reaction of unsaturated fatty acids, and its industrial production process is almost standardized in the industry, and usually unsaturated fatty acids with 11 to 22 carbon atoms are It is obtained by dimerization with a clay catalyst or the like.
  • Industrially obtained dimer acid is mainly composed of dibasic acid with 36 carbon atoms obtained by dimerizing unsaturated fatty acids with 18 carbon atoms such as oleic acid and linoleic acid. Depending on the requirements, it contains any amount of monomeric acid (18 carbon atoms), trimer acid (54 carbon atoms), other polymerized fatty acids of 20 to 54 carbon atoms.
  • dimer acid whose dimer acid content has been increased to 90% by mass or more by molecular distillation.
  • the dimer acid when a double bond remains after the dimerization reaction, the dimer acid further includes a hydrogenation reaction to lower the degree of unsaturation.
  • the polymer By having the structure derived from the dimer acid-type diamine, the polymer can be endowed with properties derived from the skeleton of the dimer acid, specifically the following properties. Since the dimer acid-type diamine is an aliphatic containing a plurality of isomeric structures of macromolecules having a molecular weight of about 500 to 620, the molar volume of the polymer is increased and the amount of polar groups in the polymer is relatively reduced. can be reduced. Such characteristics of the dimer acid-type diamine are considered to contribute to improving the dielectric properties while suppressing the deterioration of the heat resistance of the present polymer.
  • the dimer acid-type diamine has two freely moving hydrophobic chains having 4 to 9 carbon atoms and two linear aliphatic amino groups having a length close to 8 to 10 carbon atoms
  • the dimer The acid-type diamine-derived structure not only provides flexibility to the polymer, but also allows the polymer to have an asymmetric or non-planar chemical structure. Therefore, it is considered that the solubility of the present polymer can be improved.
  • dimer diamine a compound having an active hydrogen equivalent of 130-140 and an amine value of 180-220 is preferable.
  • Examples of commercial products of dimer acid type diamines include Versamine 551 (manufactured by BASF Japan Ltd.), Versamine 552 (manufactured by Cognix Japan Co., Ltd.; hydrogenated product of Versamine 551), Priamine 1075 and Priamine 1074 (both of which are Croda Japan Co., Ltd.) can be mentioned.
  • Halogen atoms for R′, R 1 and R 2 include, for example, fluorine, chlorine, bromine and iodine atoms.
  • hydrocarbon groups having 1 to 20 carbon atoms in R', R 1 and R 2 include monovalent chain hydrocarbon groups, monovalent alicyclic hydrocarbon groups and monovalent aromatic hydrocarbon groups. , or groups in which these groups are combined.
  • the heterocyclic aliphatic groups having 3 to 20 carbon atoms for R', R 1 and R 2 include monovalent heterocyclic aliphatic groups.
  • the heterocyclic aromatic group having 3 to 20 carbon atoms for R', R 1 and R 2 includes monovalent heterocyclic aromatic groups.
  • Examples of the monovalent chain hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and n-pentyl group.
  • alkenyl groups such as ethenyl group, propenyl group, butenyl group and pentenyl group; and alkynyl groups such as ethynyl group, propynyl group, butynyl group and pentynyl group.
  • Examples of the monovalent alicyclic hydrocarbon group include monocyclic cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group; polycyclic cycloalkyl groups such as norbornyl group and adamantyl group; monocyclic cycloalkenyl groups such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group and cyclohexenyl group; and polycyclic cycloalkenyl groups such as norbornenyl group.
  • Examples of the monovalent aromatic hydrocarbon group include aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, and anthryl group.
  • groups obtained by combining these groups include aralkyl groups such as a benzyl group, a phenethyl group, a phenylpropyl group, and a naphthylmethyl group.
  • Examples of the monovalent heterocyclic aliphatic group include aziridine, oxirane, thiirane, azetidine, oxetane, thietane, pyrrolidine, pyrroline, piperidine, piperidine, pyrazolidine, imidazolidine, imidazoline, tetrahydrofuran, dioxolane, tetrahydrothiophene, piperazine. , tetrahydropyran, dioxane, and morpholine-derived monovalent heterocyclic aliphatic groups.
  • Examples of the monovalent heterocyclic aromatic group include thiophene, benzothiophene, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, indole, isoindole, benzimidazole, purine, indazole, quinoline, Heterocyclic monovalent compounds such as isoquinoline, quinoxaline, quinazoline, cinnoline, furan, benzofuran (1-benzofuran), isobenzofuran (2-benzofuran), oxazole, isoxazole, thiazole, benzoxazole, benzisoxazole, benzothiazole, etc. Heterocyclic aromatic groups are included.
  • Substituents in the structure derived from dimer diamine, and substituents in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic aromatic group having 3 to 20 carbon atoms in R′, R 1 and R 2 are particularly Examples include, but are not limited to, allyl groups, halogen atoms, monovalent hydrocarbon groups having 1 to 20 carbon atoms, monovalent halogenated hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, carbon alkoxycarbonyl group having 1 to 20 carbon atoms, alkylthio group having 1 to 20 carbon atoms, nitro group, cyano group, carboxy group, sulfonic acid group, phosphonic acid group, phosphoric acid group, hydroxy group, primary to tertiary amino group, carboxy group salts, sulfonic acid group salts, phosphonic acid group salts, phosphoric acid group salts, hydroxy group salts, primary to tertiary amino group salts
  • a hydrogen atom is preferable as R'.
  • R 1 or R 2 is a hydrogen atom
  • the hydrogen atom interacts with the heteroatom site other than the nitrogen atom to which the hydrogen atom is bonded or the triazine ring site through hydrogen bonding, resulting in relatively This is preferable because the polymer tends to have excellent adhesion to the material.
  • the number of repeating units of the repeating unit represented by formula (1) is not particularly limited, it is, for example, 2 to 10,000, preferably 3 to 8,000, and more preferably 3 to 5,000.
  • the lower limit of the content of the repeating unit represented by formula (1) in the present polymer is preferably 5 mol%, more preferably 15 mol%, still more preferably 25 mol%, and particularly preferably 40 mol%.
  • the upper limit of the content is preferably 95 mol%, more preferably 90 mol%, still more preferably 85 mol%, and particularly preferably 80 mol%.
  • the polymer containing the repeating unit represented by the formula (1) in the above range has excellent solubility in solvents and excellent applicability to substrates.
  • Polymer (1) may contain structural units other than the repeating unit represented by formula (1).
  • the other structural unit is not particularly limited as long as it does not impair the effects of the present invention, but it is particularly preferred to contain a repeating unit represented by the following formula (2).
  • the polymer (2) contains a repeating unit represented by the above formula (1) and a repeating unit represented by the following formula (2).
  • R′, R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted A heterocyclic aliphatic group having 3 to 20 carbon atoms substituted by or an unsubstituted or substituted heterocyclic aromatic group having 3 to 20 carbon atoms, and R 4 has 6 carbon atoms -30 divalent aromatic hydrocarbon group, C5-20 divalent alicyclic hydrocarbon group, C1-20 divalent chain hydrocarbon group, -( R41 -O) a divalent group represented by m- , a divalent silicon-containing group, a group in which two or more selected from these groups are combined, at least part of these groups are oxygen atoms, nitrogen atoms and sulfur A group substituted with at least one selected from atoms, or a group partially substituted with a substituent, R 41 is independently an alkylene having 2 to 4 carbon atoms,
  • R′, R 1 and R 2 in formula (2) are the same as those of R′, R 1 and R 2 in formula (1).
  • R 4 is a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, a group in which the aromatic hydrocarbon group is combined with one or more other groups, at least part of these groups being oxygen atoms , a group substituted with at least one selected from a nitrogen atom and a sulfur atom, or a group partially substituted with a substituent, -NR'-R 4 in formula (2)
  • Examples of the structure of the -NR'- portion include structures derived from the compounds shown below.
  • R 4 is a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, a group in which the alicyclic hydrocarbon group is combined with one or more other groups, at least a part of these groups -NR'- in the formula (2) when a group substituted with at least one selected from an oxygen atom, a nitrogen atom and a sulfur atom, or a group partially substituted by a substituent of these groups
  • Examples of the structure of the R 4 -NR'- portion include the structures shown below.
  • the dotted line in the structure below means a bond of the nitrogen atom in -NR' of formula (2) that bonds to a group different from R 4 and R'.
  • Examples of the divalent chain hydrocarbon group having 1 to 20 carbon atoms for R 4 include a divalent group obtained by removing one hydrogen atom from the above monovalent chain hydrocarbon group.
  • R 4 is a divalent chain hydrocarbon group having 1 to 20 carbon atoms, a group in which the chain hydrocarbon group is combined with one or more other groups, and at least part of these groups are oxygen atoms , a group substituted with at least one selected from a nitrogen atom and a sulfur atom, or a group partially substituted with a substituent, -NR'-R 4 in formula (2)
  • Examples of the structure of the -NR'- portion include the structures shown below.
  • the dotted line in the structure below means a bond of the nitrogen atom in -NR' of formula (2) that bonds to a group different from R 4 and R'.
  • R 41 is independently an alkylene having 2 to 4 carbon atoms
  • m is an integer of 1 to 70, preferably 1 to 40 is an integer.
  • examples of the structure of the —NR′—R 4 —NR′- moiety in formula (2) include KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd.), Structures derived from X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-1660B-3, X-22-9409.
  • the structure of -NR'-R 4 -NR'- in formula (2) is preferably, for example, the structure shown below.
  • the dotted line in the structure below means a bond of the nitrogen atom in -NR' of formula (2) that bonds to a group different from R 4 and R'.
  • a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, a chain divalent hydrocarbon group having 1 to 20 carbon atoms, -(R 41 —O) m — is a divalent group, a divalent silicon-containing group, or at least a portion of a group in which two or more selected from these groups are combined is an oxygen atom, a nitrogen atom and sulfur
  • Specific examples of the group substituted with at least one selected from atoms include the aromatic hydrocarbon group, alicyclic hydrocarbon group, chain hydrocarbon group, oxyalkylene group, and part of the silicon-containing group.
  • R 4 is a group in which a part of a divalent chain hydrocarbon group having 1 to 20 carbon atoms is substituted with —O—, or a divalent group represented by —(R 41 —O) m — group
  • the structure of the -NR'-R 4 -NR'- moiety in formula (2) includes, for example, JEFFAMINE-D series, JEFFAMINE-ED series, JEFFAMINE-EDR series, JEFFAMINE- Examples include structures derived from polyoxyalkyleneamines such as the RT series.
  • R 4 is a group in which a part of a divalent chain hydrocarbon group having 1 to 20 carbon atoms is substituted with —O—, or a divalent group represented by —(R 41 —O) m —
  • the structure of the -NR'-R 4 -NR'- moiety in formula (2) is preferably, for example, the structure shown below.
  • the dotted line in the structure below means a bond of the nitrogen atom in -NR' of formula (2) that bonds to a group different from R 4 and R'.
  • Substituents in groups partially substituted with at least one selected from atoms, nitrogen atoms and sulfur atoms are not particularly limited, but allyl groups, halogen atoms, and 1 to 20 carbon atoms monovalent hydrocarbon group, monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, alkoxycarbonyl group having 1 to 20 carbon atoms, alkylthio group having 1 to 20 carbon atoms , nitro group, cyano group, carboxy group, sulfonic acid group, phosphonic
  • —N(R′)—R 4 — is a divalent monocyclic nitrogen-containing heterocyclic group having 5 to 8 ring atoms in which R′ and R 4 are bonded to each other.
  • the structure of the -NR'-R 4 -NR'- moiety in formula (2) is includes, for example, the structures shown below.
  • the dotted line in the structure below means a bond of the nitrogen atom in -NR' of formula (2) that bonds to a group different from R 4 and R'.
  • -N(R')-R 4 -N(R')- is a divalent monocyclic nitrogen-containing heterocyclic heterocycle having 5 to 20 ring atoms in which two R's are bonded to each other. It may be a cyclic group, and in this case, the structure of the --NR'--R 4 --NR'- portion in formula (2) includes, for example, the structures shown below.
  • the dotted line in the structure below means a bond of the nitrogen atom in -NR' of formula (2) that bonds to a group different from R 4 and R'.
  • the number of repeating units of the repeating unit represented by formula (2) is not particularly limited, but is, for example, 2 to 10,000, preferably 3 to 8,000, more preferably 3 to 5,000.
  • the lower limit of the content of the repeating unit represented by formula (2) in the present polymer is preferably 5 mol%, more preferably 15 mol%, still more preferably 25 mol%, and particularly preferably 40 mol%.
  • the upper limit of the content is preferably 95 mol%, more preferably 85 mol%, even more preferably 80 mol%, and particularly preferably 75 mol%.
  • the content of the repeating unit represented by the formula (2) is within the above range, and the solubility in various solvents and the compatibility with other components such as curable compounds described later are controlled. can do.
  • the polymers (1) and (2) may contain structural units other than the repeating units represented by the formula (1) and the repeating units represented by the formula (2).
  • the other structural unit is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include the terminal groups described above.
  • the polymer (3) has the terminal group at the terminal of the polymer (1) or the polymer (2).
  • terminal group examples include reactive groups selected from phenolic hydroxyl groups, allyl groups, vinyl groups, (meth)acryloyl groups, maleimide groups, propargyl groups and ethynyl groups, aromatic hydrocarbon groups, and aliphatic hydrocarbon groups. , a heterocyclic group.
  • the two groups at the ends of the main chain in the polymer may be the same or different.
  • terminal groups include groups derived from terminal blocking agents shown below.
  • terminal blocking agents include aminophenol compounds such as 4-(2-aminoethyl)phenol and aminophenol; allyl compounds such as allylamine, diallylamine and 4-allylphenol; chloromethylstyrene, 4-aminostyrene, 4 -Vinyl compounds such as vinylphenol and 4-isopropenylphenol; (meth)acrylic compounds such as (meth)acryloyl chloride and (meth)acrylic anhydride; maleimide compounds such as 4-hydroxyphenylmaleimide; propargyl compounds such as propargylamine ; Ethynyl compounds such as 4-ethynylaniline; Aromatic hydrocarbon group-containing compounds (e.g., monophenol compounds such as 2-phenylphenol, aniline, aromatic monoamino compounds such as 4-tert-butylaniline), aliphatic hydrocarbons Group-containing compounds (e.g., aliphatic monoamino compounds such as
  • the terminal group is selected from aminophenol compounds, allyl compounds, vinyl compounds and (meth)acrylic compounds from the viewpoint that a thermosetting composition that can react with an epoxy resin or the like can be easily obtained.
  • a reactive group derived from a terminal blocking agent is preferred.
  • the terminal group is preferably a group derived from a terminal blocking agent selected from monophenol compounds, aromatic monoamino compounds, aliphatic monoamino compounds, and cyclic amine compounds from the viewpoint of use as a thermoplastic material.
  • the present polymer has a polystyrene-equivalent weight average molecular weight (Mw) of preferably 1,000 to 400,000, more preferably 3,000 to 200,000, because it is a polymer having excellent heat resistance. and the molecular weight distribution (Mw/Mn) is preferably 1.5 to 12.0, more preferably 1.7 to 9.0. Specifically, the Mw can be measured by the method described in Examples below.
  • the glass transition temperature (Tg) of the present polymer measured by a differential scanning calorimeter (DSC) is preferably -50 to 200°C, more preferably -50 to 150°C.
  • the Tg can be measured by the method described in Examples below.
  • the 5% mass loss temperature (Td5) of the polymer measured by thermogravimetric analysis (TGA) is preferably 200 to 600°C, more preferably 250 to 600°C.
  • the polymer having Td5 in the above range can be said to be a polymer having excellent heat resistance.
  • the Td5 can be measured by the method described in Examples below.
  • the present polymer is soluble in general-purpose solvents and has excellent solubility in general-purpose solvents.
  • the general-purpose solvent includes, for example, a solvent having a boiling point of 180° C. or less under atmospheric pressure, and specific examples thereof include cyclohexanone and cyclopentanone.
  • 1 g or more of the polymer dissolves in 100 g of the general-purpose solvent at 25° C.
  • the polymer can be said to be soluble in the general-purpose solvent. Whether or not it dissolves can be determined by the presence or absence of precipitates.
  • a solution obtained by dissolving the present polymer in the general-purpose solvent can be obtained, and the solution is excellent in coatability and drying properties, which is preferable.
  • the dielectric loss tangent (tan ⁇ ) of the present polymer is preferably 0.0060 or less, more preferably 0.0050 or less, from the viewpoint of reducing transmission loss when a composition containing the present polymer is formed.
  • the lower limit is not particularly limited, it is preferably 0.0005 or more.
  • the dielectric loss tangent can be measured by the method described in Examples below.
  • the present polymer can be produced, for example, by utilizing a condensation reaction between a conventionally known dihalogenated triazine compound and a compound having a nucleophilic functional group represented by a diamine compound. Although it is as specifically described in an Example, the example is shown below.
  • Polymer (1) is prepared, for example, by combining a compound represented by the following formula (A) and a dimer diamine represented by the following formula (B) in the presence of an alkali metal compound such as potassium carbonate, cyclohexanone, N- It can be synthesized by polymerization by heating in a suitable organic solvent such as methyl-2-pyrrolidone (NMP) or N,N-dimethylacetamide (DMAc).
  • NMP methyl-2-pyrrolidone
  • DMAc N,N-dimethylacetamide
  • the polymer (2) is, for example, a compound represented by the following formula (A), a compound represented by the following formula (B), and a compound represented by the following formula (C) combined with potassium carbonate or the like.
  • It can be synthesized by heating and polymerizing in an appropriate organic solvent such as cyclohexanone, N-methyl-2-pyrrolidone (NMP) or N,N-dimethylacetamide (DMAc) in the presence of an alkali metal compound. Further, when synthesizing these, the reaction may be performed in the presence of the terminal blocking agent, and the polymer (3) is synthesized by using the terminal blocking agent during these syntheses. can do.
  • an appropriate organic solvent such as cyclohexanone, N-methyl-2-pyrrolidone (NMP) or N,N-dimethylacetamide (DMAc)
  • NMP N-methyl-2-pyrrolidone
  • DMAc N,N-dimethylacetamide
  • R 1 and R 2 are each independently synonymous with R 1 and R 2 in Formula (1), and X is a halogen atom.
  • —NR 1 R 2 may be a nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which R 1 and R 2 are bonded to each other.
  • R 4 and R' are each independently synonymous with R 4 and R' in formula (2), and -N(R')-R 4 - is R' and R 4 may be a divalent monocyclic nitrogen-containing heterocyclic group having 5 to 20 ring atoms, wherein —N(R′)—R 4 —N(R′)— is 2 may be a divalent monocyclic nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which two R' are bonded to each other. ]
  • the heating conditions are not particularly limited as long as the polymerization reaction proceeds.
  • the time is preferably 0.5-100 hours, more preferably 1-24 hours.
  • the heating temperature is preferably about 40 to 110° C. and the heating time is 4 to 24 hours, in order to obtain the present polymer with little coloration.
  • the heating temperature is more preferably 50 to 100° C. from the viewpoint of obtaining a polymer.
  • the ratio of the compound represented by the formula (A) to the total amount of the compounds represented by the formulas (B) and (C) is the compound represented by the formula (A) and the compound represented by the formula (B).
  • the compound represented by the formula (A) is preferably 30 mol% or more and 70 mol% or less, more preferably 35 mol % or more and 60 mol % or less, more preferably 35 mol % or more and 55 mol % or less
  • the compounds represented by formulas (B) and (C) are preferably 30 mol % or more and 70 mol % or less, more preferably is 40 mol % or more and 65 mol % or less, more preferably 40 mol % or more and less than 65 mol %.
  • One of the compounds represented by formula (A) may be used, or two or more of them may be used. Also, one type of compound represented by the formula (B) may be used, or two or more types may be used, and one type of the compound represented by the formula (C) may be used. , may be used in combination of two or more.
  • alkali metal compounds include alkali metals such as lithium, potassium and sodium; alkali metal hydrides such as lithium hydride, potassium hydride and sodium hydride; alkali metal hydroxides; alkali metal carbonates such as lithium carbonate, potassium carbonate and sodium carbonate; alkali metal hydrogen carbonates such as lithium hydrogen carbonate, potassium hydrogen carbonate and sodium hydrogen carbonate; alkali metal alkoxides such as sodium ethoxide; sodium acetate , potassium acetate; alkali metal oxides such as lithium oxide; alkali metal phosphates such as trilithium phosphate, trisodium phosphate, tripotassium phosphate; alkali metal fluorides such as cesium fluoride; mentioned.
  • alkali metals such as lithium, potassium and sodium
  • alkali metal hydrides such as lithium hydride, potassium hydride and sodium hydride
  • alkali metal hydroxides alkali metal carbonates such as lithium carbonate, potassium carbonate and sodium carbonate
  • potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium bicarbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, trilithium phosphate, triphosphate Sodium, tripotassium phosphate, cesium fluoride and the like are preferred.
  • 1 type may be used for the said alkali metal compound, and 2 or more types may be used for it.
  • an organic base may be used in the reaction, and specific examples thereof include ammonia, trimethylamine, triethylamine, diisopropylmethylamine, diisopropylethylamine, N-methylpiperidine, 2,2,6,6-tetramethyl -N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine and the like.
  • One type of the organic base may be used, or two or more types may be used.
  • the amount of the alkali metal compound used is usually 1 to 1 for one -NH-R' in the compounds represented by the formulas (B) and (C). It is used in an amount of 3 equivalents, preferably 1 to 2.5 equivalents, more preferably 1.1 to 2.0 equivalents.
  • the present composition may further contain components other than the polymer (1) as long as the effects of the present invention are not impaired.
  • Such other components include, for example, a curable compound (C), a curing aid (D), a reactive diluent, a solvent, a filler, an antioxidant, a reinforcing agent, a lubricant, a flame retardant, an antibacterial agent, a coloring agent, Release agents, foaming agents, polymers other than polymer (1) and curable compound (C) (e.g.
  • polyimide polyimide, polyarylene, ester resin, phenoxy resin, phenol resin, (meth)acrylic acid ester resin , polystyrene resins, hydrogenated styrene-butadiene-styrene copolymers, hydrogenated styrene-isoprene-styrene copolymers, and other rubber-like resins).
  • polystyrene resins hydrogenated styrene-butadiene-styrene copolymers
  • hydrogenated styrene-isoprene-styrene copolymers and other rubber-like resins.
  • Each of these other components may be used alone or in combination of two or more.
  • the present composition may contain a curable compound (C) (hereinafter also referred to as “compound (C)”), and from the viewpoint that a cured product having excellent chemical resistance can be easily formed, the compound (C ) is preferably included.
  • the compound (C) is a compound other than the present polymer. Since the present polymer has excellent compatibility with the compound (C), the present composition without precipitation or phase separation can be easily obtained.
  • the compound (C) contained in the present composition may be one kind or two or more kinds.
  • the curable compound (C) is a compound that is cured by irradiation with heat or light (e.g., visible light, ultraviolet light, near-infrared rays, far-infrared rays, electron beams), and requires a curing aid (D) described later.
  • heat or light e.g., visible light, ultraviolet light, near-infrared rays, far-infrared rays, electron beams
  • curing aid (D) described later.
  • examples of such compounds (C) include epoxy compounds, cyanate ester compounds, vinyl compounds, silicone compounds, oxazine compounds, maleimide compounds, allyl compounds, oxetane compounds, methylol compounds, (meth)acrylic compounds, oxazoline compounds, urethane compounds, compounds, propargyl compounds.
  • epoxy compounds, cyanate ester compounds, vinyl compounds, silicone compounds, oxazine compounds, maleimide compounds, allyl compounds, and oxetanes are particularly preferred from the viewpoint of compatibility with the polymer (1) and properties such as heat resistance. It is preferably at least one selected from the group consisting of compounds, methylol compounds, (meth)acrylic compounds, oxazoline compounds and propargyl compounds.
  • a (meth)acrylic compound means an acrylic compound and/or a methacrylic compound.
  • the epoxy compound is a compound having an epoxy group, and is a bifunctional or higher polyfunctional epoxy compound having two or more epoxy groups or a total of two or more epoxy groups and other reactive groups.
  • Specific examples include epoxy compounds represented by the following formulas (c1-1) to (c1-9).
  • Examples of the other reactive groups include alkoxysilyl groups, propargyl groups, and (meth)acryl groups.
  • Examples of the compound represented by the following formula (c1-6) include epoxy group-containing NBR particles “XER-81” manufactured by JSR Corporation.
  • epoxy compound examples include polyglycidyl ether of dicyclopentadiene-phenol polymer, phenol novolac type liquid epoxy compound, cresol novolak type epoxy compound, epoxidized styrene-butadiene block copolymer, and 3',4'-epoxy. Cyclohexylmethyl-3,4-epoxycyclohexane carboxylate and the like are also included.
  • n is 0 to 5000, and m is independently 0 to 5000.
  • R' is an alkylene group having 2 to 10 carbon atoms.
  • Examples of the cyanate ester compound include compounds represented by the following formulas (c2-1) to (c2-7).
  • n is independently 0 to 30.
  • vinyl compound examples include compounds represented by the following formulas (b-1-1) to (b-1-5).
  • the vinyl compounds further include styrene-based thermoplastic elastomers such as styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), styrene-butadiene elastomer (SBR), tert-butylstyrene, 2-vinyl- Also included are vinyl group-containing compounds such as 4,6-diamino-1,3,5-triazine, TA100 (manufactured by Mitsubishi Gas Chemical Company, Inc.), ULL-950S (manufactured by LONZA), and the like.
  • SBS styrene-butadiene-styrene copolymer
  • SIS styrene-isoprene-styrene copolymer
  • n is independently 1 to 5,000.
  • l, m and n are each independently 1-5000.
  • silicone compound examples include compounds represented by the following formulas (c4-1) to (c4-16).
  • R in formula (c4-1) one of the following is selected, and when a group having an acryloyl group is selected, it can be treated as the acrylic compound, and a group having a methacryloyl group is selected. When a group having an oxetane group is selected, it can be treated as the oxetane compound.
  • each R is independently an organic group selected from an alkyl group, an alicyclic saturated hydrocarbon group, an aryl group, and an alkenyl group, and n is It is an integer from 0 to 1000 (preferably an integer from 0 to 100).
  • Examples of the alkyl group, alicyclic saturated hydrocarbon group, aryl group, and alkenyl group include the same groups as those exemplified in the description of R′, R 1 and R 2 in formula (1) above. be able to.
  • oxazine compound examples include compounds represented by the following formulas (c5-1) to (c5-5), 2,2-bis(3,4-dihydro-3-methyl-2H-1,3-benzo oxazine) propane.
  • maleimide compound examples include compounds represented by the following formulas (c6-1) to (c6-5).
  • allyl compound examples include compounds represented by the following formulas (c7-1) to (c7-6).
  • the allyl compound is preferably a compound having two or more (especially 2 to 6, further 2 to 3) allyl groups.
  • Examples of the oxetane compound include compounds represented by the following formulas (c8-1) to (c8-3) and (3-ethyloxetan-3-yl)methyl methacrylate.
  • methylol compound examples include those described in JP-A-2006-178059 and JP-A-2012-226297.
  • polymethylolated melamine, 2,4,6-tris[bis(methoxymethyl)amino]-1,3,5-triazine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine melamine-based methylol compounds such as polymethylolated glycoluril, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril and other glycoluril-based methylol compounds; 3,9-bis[2-(3,5-diamino-2,4 ,6-triazaphenyl)ethyl]-2,4,8,10-tetraoxospiro[5.5]undecane, 3,9-bis[2-(3,5-diamino-2,4,6-tria zaphenyl)propyl]-2,
  • Examples of the (meth)acrylic compound include trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane PO (propylene oxide)-modified tri(meth)acrylate, tetramethylolpropane tetra(meth) ) acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth) Acrylates, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, tris(2-hydroxyethyl)isocyanate Nurate tri(meth)
  • oxazoline compound examples include 2,2′-bis(2-oxazoline), 1,4-bis(4,5-dihydro-2-oxazolyl)benzene, 1,3-bis(4,5-dihydro-2- oxazolyl)benzene.
  • propargyl compound examples include compounds represented by the following formulas (c9-1) to (c9-2).
  • the content of the compound (C) is preferably 1% by mass or more, more preferably 5% by mass, relative to the total 100% by mass of the compound (C) and the polymer. % or more, more preferably 10 mass % or more, preferably 99 mass % or less, more preferably 95 mass % or less, still more preferably 90 mass % or less.
  • the content of the compound (C) is within the above range, the toughness, heat resistance, and chemical resistance of the cured product of the present composition can be further improved, which is preferable.
  • This composition may contain a curing aid (D) as needed.
  • the curing aid (D) include curing agents, thermal reaction initiators (e.g., thermal radical generators, thermal acid generators, thermal base generators), photoreaction initiators (e.g., photoradical generators, light polymerization initiators such as acid generators and photobase generators).
  • the curing aid (D) may be used singly or in combination of two or more.
  • Examples of the curing aid (D) when an epoxy compound is used as the compound (C) include amine-based curing agents, acid-based or acid anhydride-based curing agents, basic active hydrogen compounds, imidazoles, and polymercaptan-based curing agents. curing agents such as phenolic resins, urea resins, melamine resins, isocyanate-based curing agents, and Lewis acids.
  • amine curing agent examples include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, iminobispropylamine, bis(hexamethylene)triamine, 1,3,6-trisaminomethylhexane, and the like.
  • MDA mencenediamine
  • IPDA isophoronediamine
  • BDA isophoronediamine
  • NDA bis(4-amino-3-methylcyclohexyl)methane, diaminodicyclohexylmethane, bisaminomethylcyclohexane, 3,9-bis(3-aminopropyl)-
  • Cycloaliphatic polyamines such as 2,4,8,10-tetraoxaspiro[5.5]undecane, norbornane skeleton diamines represented by NBDA manufactured by Mitsui Chemicals, Inc.
  • Aliphatic polyamines containing aromatic rings aromatic polyamines such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldiphenylmethane, and derivatives thereof.
  • amine-based curing agents include, for example, Mannich-modified amines obtained by reacting polyamines with aldehydes and/or phenols; amine adducts (polyamine epoxy resin adducts), polyamine-ethylene oxide adducts, polyamine-propylene oxide adducts.
  • cyanoethylated polyamines which are reaction products of aliphatic polyamines and ketones; tetramethylguanidine, triethanolamine, piperidine, pyridine, 4-dimethylaminopyridine, benzyldimethylamine, picoline, 2-(dimethylaminomethyl)phenol , dimethylcyclohexylamine, dimethylbenzylamine, dimethylhexylamine, dimethylaminophenol, dimethylamino-p-cresol, N,N'-dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, 2,4, Secondary or tertiary amines such as 6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5.4.0]-7-undecene; dimer acid, diethylenetriamine, triethylenetetramine, etc. and a liquid polyamide obtained by reacting with a polyamine.
  • Examples of the acid-based or acid anhydride-based curing agent include polycarboxylic acids such as adipic acid, azelaic acid and decanedicarboxylic acid; phthalic anhydride, trimellitic anhydride, ethylene glycol bis(anhydrotrimellitate); Aromatic acid anhydrides such as glycerol tris (anhydrotrimellitate), pyromellitic anhydride, 3,3′,4,4′-benzophenonetetracarboxylic anhydride; maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride Acid, methyltetrahydrophthalic anhydride, methylnadic anhydride, alkenylsuccinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylcyclohexenetetracarboxylic anhydride, methylhimic anhydride, trialkyltetrahydrophthalic an
  • Examples of the basic active hydrogen compound include dicyandiamide and organic acid dihydrazide.
  • imidazoles examples include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1- Cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-methylimidazolium isocyanurate, 2,4-diamino-6-[2-methylimidazoline-(1)]-ethyl-S -triazine, 2,4-diamino-6-[2-ethyl-4-methylimidazoline-(1)]-ethyl-S-triazine.
  • polymercaptan curing agent examples include partial epoxy adducts of 2,2'-bismercaptoethyl ether; pentaerythritol tetrathioglycolate, dipentaerythritol hexathioglycolate, trimethylolpropane tristhioglycolate, and the like.
  • isocyanate-based curing agent examples include isocyanate compounds such as toluene diisocyanate, hexamethylene diisocyanate, and xylene diisocyanate; and blocked isocyanate compounds obtained by masking isocyanate groups by reacting them with blocking agents such as phenol, alcohol, and caprolactam. mentioned.
  • Lewis acid examples include diaryliodonium salts and triarylsulfonium salts.
  • the curing aid (D) includes an onium salt compound, a sulfone compound, a sulfonic acid ester compound, a sulfonimide compound, a disulfonyldiazomethane compound, a disulfonylmethane compound, and an oxime sulfonate.
  • an onium salt compound a sulfone compound, a sulfonic acid ester compound, a sulfonimide compound, a disulfonyldiazomethane compound, a disulfonylmethane compound, and an oxime sulfonate.
  • photoacid generators such as organic halides and disulfones can also be used.
  • Examples of the curing aid (D) when a cyanate ester compound is used as the compound (C) include zinc octylate, zinc naphthenate, cobalt naphthenate, copper naphthenate, iron acetylacetonate, nickel octylate, manganese octylate, and the like.
  • organic metal salts phenol, xylenol, cresol, resorcinol, catechol, octylphenol, phenol compounds such as nonylphenol, alcohols such as 1-butanol and 2-ethylhexanol, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Imidazoles such as phenyl-4-methyl-5-hydroxymethylimidazole and derivatives such as adducts of carboxylic acids or acid anhydrides of these imidazoles, benzyldimethylamine, 4-methyl-N,N-dimethylbenzylamine Phosphorus compounds such as amines, phosphine-based compounds,
  • Examples of the curing aid (D) when using a vinyl compound as the compound (C) include compounds (polymerizing agents) that generate cationic or radical active species by heat or light.
  • Cationic polymerization agents include, for example, diaryliodonium salts and triarylsulfonium salts.
  • Examples of radical polymerization agents include benzoin-based compounds such as benzoinacetophenone, acetophenone-based compounds such as 2,2-dimethoxy-2-phenylacetophenone, sulfur-based compounds such as 2,4-diethylthioxanthone, and azobisisobutyronitrile. and azo compounds such as 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and organic peroxides such as dicumyl peroxide.
  • Examples of the curing aid (D) when a vinyl compound is used as the compound (C) include acetophenone, propiophenone, benzophenone, xanthol, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylactophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4' -dimethoxybenzophenone, 4-chloro-4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoin, benzoin methyl ether, benzoin butyl ether, bis(4-dimethylamino Photo
  • Examples of the curing aid (D) when a silicone compound is used as the compound (C) include platinum black, platinum chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, chloroplatinic acid and Complexes with olefins, platinum-based catalysts such as platinum bisacetoacetate; platinum-group metal catalysts such as palladium-based catalysts; rhodium-based catalysts; zinc benzoate and zinc octylate can be used.
  • Examples of the curing aid (D) when a silicone compound is used as the compound (C) include acetophenone, propiophenone, benzophenone, xanthol, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylactophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4'- Dimethoxybenzophenone, 2,2'-diethoxyacetophenone, 4-chloro-4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoin, benzoin methyl ether, benzoin Butyl ether,
  • Examples of the curing aid (D) when an oxazine compound is used as the compound (C) include phenol and derivatives thereof, cyanate esters, Bronsted acids such as p-toluenesulfonic acid, adipic acid, and p-toluenesulfonic acid. Curing agents such as esters, 4,4'-diaminodiphenylsulfone, aromatic amine compounds such as melamine, bases such as 2-ethyl-4-methylimidazole, boron trifluoride, and Lewis acids can be used. Furthermore, the photoacid generator and photobase generator explained as the curing aid (D) in the case of using the epoxy compound can also be used.
  • Examples of the curing aid (D) when a maleimide compound is used as the compound (C) include imidazole, 1-methylimidazole, 1-benzyl-2-methylimidazole, 2-methylimidazoline, N,N-diisopropylethylamine, 1,4-dimethylpiperazine, quinoline, triazole, benzotriazole, bases such as DBU, phosphorus compounds such as triphenylphosphine, curing agents such as azobisisobutyronitrile, 2,5-dimethyl-2,5-di( Organic peroxides such as t-butylperoxy)hexane and dicumyl peroxide can be used. Furthermore, the photoacid generator and photobase generator explained as the curing aid (D) in the case of using the epoxy compound can also be used.
  • Examples of the curing aid (D) when an allyl compound or propargyl compound is used as the compound (C) include azo initiators such as azobisisobutyronitrile and dimethyl 2,2'-azobisisobutyrate, ketone peroxides, Peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, peroxyester, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumyl peroxide, etc.
  • azo initiators such as azobisisobutyronitrile and dimethyl 2,2'-azobisisobutyrate, ketone peroxides, Peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, peroxyester, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumyl peroxide, etc
  • acetophenones such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1,1'-hydroxycyclohexylphenyl ketone, benzoin such as benzoin and benzoin ethyl ether, benzophenone benzophenone-based curing agents such as acylphosphine oxide; sulfur-based curing agents such as thioxanthone; benzyl-based curing agents such as benzyl and 9,10-phenanthrenequinone; and peroxycarbonate-based curing agents.
  • the photoacid generator and photobase generator explained as the curing aid (D) in the case of using the epoxy compound can also be used.
  • the curing aid (D) in the case of using an oxetane compound or a methylol compound as the compound (C), for example, a light or thermal cation generator can be used.
  • photocation generators include onium salt compounds, halogen-containing compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, and diazomethane compounds.
  • onium salt compound, halogen-containing compound, sulfone compound, sulfonic acid compound, sulfonimide compound and diazomethane compound are described in paragraphs [0074] to [0079] of JP-A-2014-186300. compound.
  • halogen-containing compounds include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds.
  • preferred halogen-containing compounds include 1,10-dibromo-n-decane, 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane; phenyl-bis(trichloromethyl)-s-triazine , 4-methoxyphenyl-bis(trichloromethyl)-s-triazine, styryl-bis(trichloromethyl)-s-triazine, naphthyl-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran -2-yl)ethenyl]-4,6-bis-(trichloromethyl)-1,3,5-triazine and other s-triazine derivatives.
  • the content of the curing aid (D) is preferably within a range in which the composition can be cured satisfactorily to obtain a cured product.
  • the content of the curing aid (D) is usually 0.1 parts by mass or more and 30 parts by mass or less, preferably 0.1 part by mass, with respect to a total of 100 parts by mass of the polymer and the compound (C).
  • the amount is from 0.1 part by mass to 20 parts by mass, preferably from 0.1 part by mass to 15 parts by mass.
  • the composition may contain a solvent, if desired.
  • the solvent include N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and the like.
  • Amide solvents ⁇ -butyrolactone, ester solvents such as butyl acetate; ketone solvents such as cyclopentanone, cyclohexanone, methyl ethyl ketone, benzophenone, 1,2-methoxyethane, diphenyl ether, tetrahydrofuran, 4-methyltetrahydropyran, dioxane, etc.
  • ether solvents such as 1-methoxy-2-propanol and propylene glycol methyl ether acetate; sulfolane, dimethylsulfoxide, diethylsulfoxide, dimethylsulfone, diethylsulfone, diisopropylsulfone and diphenylsulfone; methylene chloride, benzene, toluene, xylene, dialkoxybenzene (alkoxy group: 1 to 4 carbon atoms), trialkoxybenzene (alkoxy group: 1 to 4 carbon atoms).
  • solvents may be used individually by 1 type, and may be used 2 or more types.
  • the content of the solvent in the present composition is not particularly limited, but for example, with respect to a total of 100 parts by mass of the polymer and compound (C), preferably 0 parts by mass or more and 2000 parts by mass or less, more preferably 0 parts by mass part or more and 1000 parts by mass or less.
  • This composition may contain a filler as needed. Since the polymer contained in the composition has a triazine ring structure, it has a planar structure with strong pi-electron interaction. Therefore, it is considered that the present polymer has a high coordinating ability to fillers and the like. In addition, part of the main chain has a structure derived from dimer diamine, and it is thought that the flexible long main chain can follow the particle surface and particle gaps such as fillers. When it contains, it is thought that a composition having excellent dispersibility of the filler can be easily obtained. As described above, the present polymer is considered to have excellent coordinating ability and dispersibility, as well as excellent dispersion stability, and thus to function as a good dispersant.
  • filler conventionally known fillers can be used, and the filler may be appropriately selected from conventionally known fillers according to the application of the present composition.
  • a filler may be used individually by 1 type, and may use 2 or more types.
  • Examples of the filler include at least one selected from the group consisting of metals, carbon, metal carbides, metal oxides and metal nitrides, with metal oxides and metal nitrides being preferred.
  • metal oxides include magnesium oxide, aluminum oxide (alumina), silicon oxide (solid silica, hollow silica), calcium oxide, zinc oxide, yttrium oxide, zirconium oxide, cerium oxide, ytterbium oxide, sialon (silicon, ceramics composed of aluminum, oxygen, and nitrogen).
  • Examples of metal nitrides include boron nitride, aluminum nitride and silicon nitride.
  • the shape of the filler is not particularly limited, and may be particulate, whisker-like, fibrous, plate-like, or aggregates thereof.
  • fillers include silica having a silanol group (--SiOH) at the end such as ADMAFINE SC2500-SQ manufactured by Admatechs Co., Ltd., silica having an aminophenyl group such as ADMAFINE SC2500-SXJ manufactured by the same company, and silica manufactured by the same company.
  • silica having a silanol group (--SiOH) at the end such as ADMAFINE SC2500-SQ manufactured by Admatechs Co., Ltd.
  • silica having an aminophenyl group such as ADMAFINE SC2500-SXJ manufactured by the same company
  • silica manufactured by the same company such as ADMAFINE SC2500-SQ manufactured by Admatechs Co., Ltd.
  • Silica having a phenyl group such as ADMAFINE SC2500-SPJ, boron nitride powder such as XGP, SGP and MGP manufactured by Denka Co., Ltd., boron nitride powder such as UHP-1K and UHP-2K manufactured by Showa Denko Co., Ltd., Denka ( Spherical alumina powder such as DAW-01, DAW-01DC, DAW-03 and DAW-05 manufactured by Showa Denko K.K.
  • ADMAFINE SC2500-SQ and ADMAFINE SC2500-SPJ are preferably used.
  • the content ratio of the filler may be appropriately selected according to the application of the present composition. , more preferably 10 to 9000 parts by mass.
  • the composition may optionally contain a reactive diluent.
  • the reactive diluent is a liquid compound that reacts with the curable compound (C) and dissolves other components when the composition is formed, or is mixed uniformly. preferable.
  • Such a reactive diluent may be appropriately selected from conventionally known reactive diluents according to the type of the curable compound (C) of the present composition. Reactive diluents may be used singly or in combination of two or more.
  • the reactive diluent for example, if the curable compound (C) is an epoxy compound, a monofunctional liquid epoxy compound that can easily react with epoxy, a liquid acid anhydride, or the like can be used.
  • the content of the reactive diluent may be appropriately selected according to the application of the present composition. It is preferably 20 to 150 parts by mass, more preferably 50 to 120 parts by mass.
  • antioxidant examples include hindered phenol-based compounds, phosphorus-based compounds, sulfur-based compounds, metal-based compounds, and hindered amine-based compounds. Among these, hindered phenol compounds are preferred.
  • An antioxidant may be used individually by 1 type, and may use 2 or more types.
  • Hindered phenolic compounds having a molecular weight of 500 or more include, for example, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[ 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino) -3,5-triazine, pentaerythritol tetrakis[3-(3,5-t-butyl-4-hydroxyphenyl)propionate], 1,1,3-tris[2-methyl-4-[3-(3, 5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-5-t-butylphenyl]butane
  • the content of the antioxidant is, for example, preferably 0.01 parts by mass or more and 10 parts by mass with respect to a total of 100 parts by mass of the polymer and the compound (C) It is below the department.
  • the preparation method of the present composition is not particularly limited, but it can be prepared, for example, by uniformly mixing the polymer (1) and, if necessary, the other components.
  • the form of the present composition can be liquid, paste, or the like.
  • a solventless composition can be obtained by dissolving it in the liquid compound (C).
  • the cured product according to one embodiment of the present invention is a cured product of the present composition described above, and is obtained by curing the present composition described above.
  • the shape of the cured product is not particularly limited, and may be an appropriate shape depending on the application, purpose, and the like.
  • the method of curing the present composition is not particularly limited, but usually a method of thermal curing by heating or a method of photocuring by irradiation with light is used. In addition, these methods can also be used together.
  • the heating temperature is preferably 50 to 350°C, more preferably 100 to 300°C, still more preferably 100 to 280°C.
  • the heating time is preferably 0.5 to 36 hours, more preferably 0.5 to 24 hours.
  • the light to be irradiated includes, for example, visible light, ultraviolet rays, near-infrared rays, far-infrared rays, and electron beams.
  • One embodiment of the cured product includes, for example, a film.
  • the film can be obtained as a film-shaped cured product, for example, by melt-molding or cast-molding the present composition.
  • the use of the film is not particularly limited, it can be suitably used as an optical film, and specifically, it can be suitably used as a liquid crystal display element substrate, a light guide plate, a polarizing film, a retardation film, and the like.
  • the thickness of the film is not particularly limited, and may be appropriately selected according to the desired application.
  • Molded Article A molded article according to one embodiment of the present invention is obtained by molding the polymer (2).
  • One embodiment of the molded article includes, for example, a film.
  • the film can be obtained as a film-shaped molding by, for example, melt molding or cast molding the polymer (2).
  • the use and thickness of the film are the same as those described in the section on the cured product.
  • Laminate A laminate according to one embodiment of the present invention is formed using a substrate and a cured product layer formed using the present composition, or a substrate and the polymer (2).
  • layer (hereinafter also referred to as “polymer layer”).
  • the laminate may have a substrate of two or more layers, may have a cured product layer or a polymer layer of two or more layers, other than the substrate and the cured product layer or polymer layer It may have other conventionally known layers.
  • the laminate has two or more substrates, a cured product layer, a polymer layer, and other layers, these may be the same layer (plate) or different layers (plates). good too.
  • the substrate examples include metal substrates, inorganic substrates (substrates other than metal substrates), resin substrates, and the like, from the viewpoint of adhesiveness and practicality.
  • the metal substrate examples include metal substrates having copper, aluminum, gold, silver, nickel, palladium, etc. as components.
  • the inorganic substrate examples include inorganic substrates having silicon, silicon carbide, silicon nitride, alumina, glass, gallium nitride, etc. as components.
  • the resin substrate include resin substrates having components such as liquid crystal polymer, polyimide, polyphenylene sulfide, polyamide (nylon), polyethylene terephthalate, polyethylene naphthalate, and polyolefin.
  • the cured product layer can be formed, for example, by applying the present composition onto a substrate and then thermally curing and/or photocuring the composition.
  • the polymer layer can be formed, for example, by disposing the polymer (2) on the substrate and then melting the polymer (2).
  • the thickness of the cured product layer and the polymer layer is not particularly limited, it is, for example, 1 ⁇ m to 3 mm.
  • the present polymer, the present composition, the cured product, the molded article and the laminate are suitable for structural materials used in the transportation industry such as the aircraft industry and the automobile industry, and electrical and electronic materials used in the electrical and electronic industry.
  • Adhesives e.g. thermally conductive adhesives, adhesive sheets); Adhesives (e.g.
  • insulating tapes, conductive tapes Structural adhesives and prepregs used for various structural materials; Various coating agents; Optical parts (e.g. wavelength plates , optical films such as retardation plates, various special lenses such as conical lenses, spherical lenses and cylindrical lenses, lens arrays); insulating films for printed wiring boards, and the like.
  • Optical parts e.g. wavelength plates , optical films such as retardation plates, various special lenses such as conical lenses, spherical lenses and cylindrical lenses, lens arrays
  • insulating films for printed wiring boards and the like.
  • Electronic Component An electronic component according to an embodiment of the present invention has the laminate described above.
  • the electronic component may have two or more laminates. If there are two or more laminates, they may each be the same or different.
  • Examples of the electronic parts include circuit boards, semiconductor packages, display boards, and the like.
  • the cured product layer and polymer layer in the laminate can be used as a surface protective film, a rewiring layer, or a flattening film for these electronic components. Since the cured material layer and the polymer layer can maintain insulation even under high temperature and high humidity, the electronic component can protect the circuit pattern from the external environment such as dust, heat, and moisture, and also provide insulation between the circuit patterns. It is highly reliable and can operate stably for many years.
  • a metal is filled by plating or the like between the patterns of the cured material layer or polymer layer, and if necessary, further cured material layers or polymer layers are laminated, and the metal is repeatedly filled to form a rewiring layer.
  • a metal is filled by plating or the like between the patterns of the cured material layer or polymer layer, and if necessary, further cured material layers or polymer layers are laminated, and the metal is repeatedly filled to form a rewiring layer. can be formed, thereby manufacturing an electronic component having a substrate and a rewiring layer containing metal wiring and an insulating film.
  • dimer diamine is not a single substance, so the structure derived from dimer diamine shown in the following formula represents its typical structure. The same applies to formulas described in the following examples.
  • Example 2 A solution of the target polymer (11) having a solid content of 30% by mass was obtained in the same manner as in Example 1, except that each component used in Example 1 was changed as follows. 2-phenylamino-4,6-dichloro-s-triazine (24.8 g), Priamine 1075 (11.0 g), 1,3-bisaminomethylcyclohexane (11.7 g), potassium carbonate (15.6 g), Cyclohexanone (88.7 g), water (22.1 g)
  • 1 H-NMR spectrum of the obtained polymer (11) is shown in FIG. From the peaks around 1.5 ppm and 0.5 ppm in the 1 H-NMR spectrum, it was confirmed that the obtained polymer (11) was a polymer having the structure represented by the formula (10). 1 H-NMR was measured as follows. 1 H-NMR of the following polymers were also measured in the same manner.
  • Example 3 The target polymer (12) represented by the following formula (12) having a solid content of 30% by mass was prepared in the same manner as in Example 1, except that each component used in Example 1 was changed as follows. A solution was obtained. 2-Phenylamino-4,6-dichloro-s-triazine (17.4 g), Priamine 1075 (19.3 g), 4,4′-methylenebis(2-methylcyclohexylamine) (isomer mixture) (8.6 g) ), potassium carbonate (11.0 g), cyclohexanone (73.9 g), water (31.7 g)
  • Example 4 The target polymer (13) represented by the following formula (13) having a solid content of 30% by mass was obtained in the same manner as in Example 1, except that each component used in Example 1 was changed as follows. A solution was obtained. 2-phenylamino-4,6-dichloro-s-triazine (15.0 g), Priamine 1075 (16.7 g), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (12.8 g) , potassium carbonate (17.3 g), cyclohexanone (117.6 g), water (60.6 g)
  • Example 5 The target polymer (14) represented by the following formula (14) having a solid content of 30% by mass was obtained in the same manner as in Example 1, except that each component used in Example 1 was changed as follows. A solution was obtained. 2-phenylamino-4,6-dichloro-s-triazine (8.4 g), Priamine 1075 (13.1 g), poly(propylene glycol) diamine (JEFFAMINE-D2000 [manufactured by Huntsman]) (21.0 g), Potassium carbonate (5.3 g), cyclohexanone (69.5 g), water (29.8 g)
  • the 1 H-NMR spectrum of the obtained polymer (14) is shown in FIG. From the 1 H-NMR spectrum, it was confirmed that the obtained polymer (14) was a polymer having the structure represented by the above formula (14).
  • Example 6 A solution of the target polymer (15) having a solid content of 30% by mass was obtained in the same manner as in Example 5, except that each component used in Example 5 was changed as follows. 2-phenylamino-4,6-dichloro-s-triazine (6.6 g), Priamine 1075 (7.5 g), poly(propylene glycol) diamine (JEFFAMINE-D2000) (27.9 g), potassium carbonate (4. 2 g), cyclohexanone (68.6 g), water (29.4 g)
  • Example 7 The target polymer (16) represented by the following formula (16) having a solid content of 30% by mass was obtained in the same manner as in Example 1, except that each component used in Example 1 was changed as follows. A solution was obtained. 2-phenylamino-4,6-dichloro-s-triazine (10.2 g), Priamine 1075 (20.3 g), amino-modified silicone oil at both ends (X-22-161B [manufactured by Shin-Etsu Chemical Co., Ltd.]) (12.6 g), potassium carbonate (6.4 g), cyclohexanone (70.4 g), water (30.2 g)
  • Example 8 A solution of the target polymer (17) having a solid content of 30% by mass was obtained in the same manner as in Example 7, except that each component used in Example 7 was changed as follows. 2-phenylamino-4,6-dichloro-s-triazine (8.1 g), Priamine 1075 (14.3 g), both terminal amino-modified silicone oil (X-22-161B) (20.1 g), potassium carbonate ( 5.1 g), cyclohexanone (69.3 g), water (29.7 g)
  • Example 9 A solution of the target polymer (18) having a solid content of 30% by mass was obtained in the same manner as in Example 7, except that each component used in Example 7 was changed as follows. 2-phenylamino-4,6-dichloro-s-triazine (10.0 g), Priamine 1075 (16.5 g), amino-modified silicone oil at both ends (X-22-161A [manufactured by Shin-Etsu Chemical Co., Ltd.]) (16.5 g), potassium carbonate (6.3 g), cyclohexanone (70.3 g), water (30.1 g)
  • the 1 H-NMR spectrum of the obtained polymer (18) is shown in FIG. Polymer (18) obtained from the peak near 0 ppm (—Si—CH 3 , 0.13 ppm, National Institute of Advanced Industrial Science and Technology: see organic compound spectrum database) of the 1 H-NMR spectrum. confirmed the structure of
  • Example 10 A solution of the target polymer (19) having a solid content of 30% by mass was obtained in the same manner as in Example 7, except that each component used in Example 7 was changed as follows. 2-phenylamino-4,6-dichloro-s-triazine (11.6 g), Priamine 1075 (15.4 g), amino-modified silicone oil at both ends (KF-8010 [manufactured by Shin-Etsu Chemical Co., Ltd.]) (16 .5 g), potassium carbonate (7.3 g), cyclohexanone (71.1 g), water (30.4 g)
  • Example 11 The target polymer (22) represented by the following formula (22) having a solid content of 30% by mass was prepared in the same manner as in Example 5 except that the components used in Example 5 were changed as follows. A solution was obtained. 4,6-dichloro-N,N-diphenyl-1,3,5-triazin-2-amine (PDCT) (10.4 g), Priamine 1075 (12.3 g), poly(propylene glycol) diamine (JEFFAMINE-D2000 ) (19.7 g), potassium carbonate (5.0 g), cyclohexanone (69.2 g), water (29.7 g)
  • PDCT 4,6-dichloro-N,N-diphenyl-1,3,5-triazin-2-amine
  • Priamine 1075 (12.3 g)
  • poly(propylene glycol) diamine JEFFAMINE-D2000
  • potassium carbonate 5.0 g
  • cyclohexanone 69.2 g
  • water 29.7 g
  • Example 12 The target polymer (23) represented by the following formula (23) having a solid content of 30% by mass was obtained in the same manner as in Example 5, except that each component used in Example 5 was changed as follows. A solution was obtained. 4,6-dichloro-N,N-dimethyl-1,3,5-triazin-2-amine (MDCT) (7.1 g), Priamine 1075 (13.7 g), poly(propylene glycol) diamine (JEFFAMINE-D2000 ) (21.9 g), potassium carbonate (5.6 g), cyclohexanone (69.7 g), water (29.9 g)
  • MDCT 4,6-dichloro-N,N-dimethyl-1,3,5-triazin-2-amine
  • Priamine 1075 (13.7 g)
  • poly(propylene glycol) diamine JEFFAMINE-D2000
  • potassium carbonate 5.6 g
  • cyclohexanone 69.7 g
  • water 29.9 g
  • Example 13 The target polymer (24) represented by the following formula (24) having a solid content of 30% by mass was obtained in the same manner as in Example 5, except that each component used in Example 5 was changed as follows. A solution was obtained. 4,6-dichloro-1,3,5-triazin-2-amine (ADCT) (6.2 g), Priamine 1075 (14.0 g), poly(propylene glycol) diamine (JEFFAMINE-D2000) (22.5 g) , potassium carbonate (5.7 g), cyclohexanone (69.8 g), water (29.9 g)
  • ADCT 4,6-dichloro-1,3,5-triazin-2-amine
  • Priamine 1075 (14.0 g)
  • poly(propylene glycol) diamine JEFFAMINE-D2000
  • potassium carbonate 5.7 g
  • cyclohexanone 69.8 g
  • water 29.9 g
  • Example 80 In a four-neck separable flask equipped with a stirrer, 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (17.8 g), dimer diamine (Priamine 1075) (19.8 g), 1, 3-bis(4-piperidyl)propane (7.8 g) and potassium carbonate (10.4 g) were weighed, cyclohexanone (60.0 g) and water (25.7 g) were added, and the mixture was stirred under a nitrogen atmosphere. , and 100° C. for 20 hours.
  • AnDCT 2-phenylamino-4,6-dichloro-s-triazine
  • Priamine 1075 dimer diamine
  • 1, 3-bis(4-piperidyl)propane 7.8 g
  • potassium carbonate 10.4 g
  • Example 81 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (20.1 g), dimer diamine (Priamine 1075) (22.4 g), piperazine ( 3.6 g) and potassium carbonate (11.8 g) were weighed, cyclohexanone (60.0 g) and water (25.7 g) were added, and the mixture was reacted at 100° C. for 20 hours under a nitrogen atmosphere. After the reaction is completed, the aqueous phase portion is separated with a separating funnel, the organic phase is washed with deionized water until it becomes neutral, and then the solvent is concentrated. A solution of polymer (26) was obtained.
  • a solution of polymer (26) was obtained.
  • Example 82 2-Phenylamino-4,6-dichloro-s-triazine (AnDCT) (19.9 g), dimer diamine (Priamine 1075) (22.0 g), homopiperazine were placed in a four-necked separable flask equipped with a stirrer. (4.1 g) and potassium carbonate (11.6 g) were weighed, cyclohexanone (60.0 g) and water (25.7 g) were added thereto, and reacted at 100° C. for 20 hours under a nitrogen atmosphere. .
  • Example 84 In a four-necked separable flask equipped with a stirrer, 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (18.5 g), dimer diamine (Priamine 1075) (20.5 g), N, N'-diethyl-1,6-diaminohexane (6.6 g) and potassium carbonate (10.8 g) are weighed, cyclohexanone (60.0 g) and water (25.7 g) are added, nitrogen The reaction was carried out at 100° C. for 20 hours in an atmosphere.
  • Example 88 4,6-Dichloro-N,N-diphenyl-1,3,5-triazin-2-amine (PDCT) (11.2 g), 2-methyl-2 were placed in a four-necked separable flask equipped with a stirrer.
  • PDCT 4,6-Dichloro-N,N-diphenyl-1,3,5-triazin-2-amine
  • 2-methyl-2 were placed in a four-necked separable flask equipped with a stirrer.
  • -phenylamino-4,6-dichloro-s-triazine (AMDCT) (9.0 g)
  • dimer diamine Principal 1075
  • 6 N,N'-diethyl-1,6-diaminohexane (6.
  • Example A1 2-Phenylamino-4,6-dichloro-s-triazine (AnDCT) (13.6 g), dimer diamine (Priamine 1075) (30.1 g), diallylamine ( 0.44 g) and potassium carbonate (7.9 g) were weighed in, cyclohexanone (60.0 g) and water (25.7 g) were added thereto, and the mixture was reacted at 100° C. for 20 hours under nitrogen atmosphere. After the reaction is completed, the aqueous phase portion is separated with a separating funnel, and the organic phase is washed with deionized water until it becomes neutral, and then the solvent is concentrated to give a solid content of 30% by mass represented by the following formula (39). A solution of polymer (39) was obtained.
  • Example A2 The target polymer (40) represented by the following formula (40) having a solid content of 30% by mass was prepared in the same manner as in Example A1 except that the components used in Example A1 were changed as follows. A solution was obtained. 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (13.5 g), dimer diamine (Priamine 1075) (29.9 g), methacrylic anhydride (0.69 g), potassium carbonate (7.9 g) )
  • Example A3 The target polymer (41) represented by the following formula (41) having a solid content of 30% by mass was obtained in the same manner as in Example A1 except that the components used in Example A1 were changed as follows. A solution was obtained. 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (13.6 g), dimer diamine (Priamine 1075) (30.1 g), acryloyl chloride (0.41 g), potassium carbonate (7.9 g)
  • Example A4 The target polymer (42) represented by the following formula (42) having a solid content of 30% by mass was prepared in the same manner as in Example A1 except that the components used in Example A1 were changed as follows. A solution was obtained. 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (13.6 g), dimer diamine (Priamine 1075) (30.1 g), chloromethylstyrene (m-, p-mixture) (0.43 g) ), potassium carbonate (7.9 g)
  • Example A5 The target polymer (43) represented by the following formula (43) having a solid content of 30% by mass was obtained in the same manner as in Example A1 except that the components used in Example A1 were changed as follows. A solution was obtained. 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (13.9 g), dimer diamine (Priamine 1075) (30.2 g), 4-(2-aminoethyl)phenol (0.16 g), Potassium carbonate (8.1g)
  • Example A6 Trichlorotriazine (11.0 g), dimer diamine (Priamine 1075) (30.1 g), and potassium carbonate (7.9 g) were weighed into a four-necked separable flask equipped with a stirrer, and cyclohexanone was added thereto. (60.0 g) and water (25.7 g) were added and reacted at 60° C. for 2 hours under nitrogen atmosphere. After completion of the reaction, diallylamine (9.0 g) and 1% by mass cyclohexane solution (5.2 g) of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl were added, and the reaction was further carried out at 100° C. for 13 hours.
  • Example A7 Trichlorotriazine (10.0 g), dimer diamine (Priamine 1075) (24.8 g), and potassium carbonate (11.5 g) were weighed into a four-necked separable flask equipped with a stirrer, and cyclohexanone was added thereto. (60.0 g) and water (25.7 g) were added and reacted at 60° C. for 2 hours under nitrogen atmosphere. After completion of the reaction, 4-(2-aminoethyl)phenol (11.7 g) and a 1 mass% cyclohexane solution (5.2 g) of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl were added. , and further reacted at 100° C. for 13 hours. After the reaction is completed, the aqueous phase portion is separated with a separating funnel, the organic phase is washed with deionized water until it becomes neutral, and then the solvent is concentrated. A solution of polymer (45) was obtained.
  • Example A8 In a four-neck separable flask equipped with a stirrer, 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (13.4 g), dimer diamine (Priamine 1075) (29.8 g), 4- Hydroxyphenylmaleimide (0.84 g) and potassium carbonate (8.5 g) were weighed, cyclohexanone (40.0 g) and water (25.7 g) were added, and the mixture was reacted at 100°C for 20 hours under a nitrogen atmosphere.
  • AnDCT 2-phenylamino-4,6-dichloro-s-triazine
  • Comparative example 1 Commercially available ULTIMID3000A (manufactured by ABC Nanotech., LTD.), which is a flexible bismaleimide oligomer, was used as Comparative Example 1 (polymer (30)).
  • Comparative example 2 Commercially available jER872 (manufactured by Mitsubishi Chemical Corporation), which is a flexible bisphenol A type epoxy resin, was used as Comparative Example 2 (polymer (31)).
  • N-methylpyrrolidone (398 g) was added for dilution, and the salt was filtered through filter paper, and the filtrate was coagulated with 10.5 kg of methanol.
  • the solidified powder is filtered off, the powder is washed again with a small amount of methanol, filtered off, and the filtrate is dried under reduced pressure at 120° C. for 12 hours using a vacuum dryer to give the following formula ( 23 g (yield: 89%) of the desired polymer (37) consisting of the repeating unit represented by 37) was obtained.
  • ⁇ Weight average molecular weight (Mw)> The weight average molecular weight (Mw) of each polymer is determined using a GPC apparatus ("HLC-8320 type, 8420 type” manufactured by Tosoh Corporation), and when the obtained polymer is dissolved in tetrahydrofuran (THF) ( Examples 1 to 13, Examples 80 to 88, and Examples A1 to A8) were measured under the following THF conditions, and when the obtained polymer was insoluble in THF (Comparative Examples 3 to 9), Measured under the following N-methyl-2-pyrrolidone conditions. As for Comparative Example 7, although it was partially insoluble in N-methyl-2-pyrrolidone, Mw was measured using the soluble portion.
  • HPC-8320 type, 8420 type manufactured by Tosoh Corporation
  • Tg Glass transition temperature
  • the glass transition temperature (Tg) of each polymer was measured using a differential scanning calorimeter (DSC device "Thermo Plus DSC8230" manufactured by Rigaku Corporation) under a nitrogen atmosphere at a temperature elevation rate of 20°C/min.
  • the temperature corresponding to the intersection of the baseline and the tangent line at the inflection point in the DSC heating curve of the thermogram was taken as the temperature.
  • the inflection point was the temperature corresponding to the peak in the DDSC curve, which is the differential curve of the DSC heating curve.
  • the DDSC curve was referred to as needed to confirm the DSC baseline.
  • TMA inflection point> For the polymer whose glass transition temperature (Tg) was difficult to measure or whose glass transition temperature was unclear, the softening point was obtained from the TMA inflection point.
  • the softening point is obtained by using a thermomechanical analyzer ("TMA7100" manufactured by Hitachi High-Tech Science Co., Ltd.) in a thermogram thermal displacement curve obtained at a heating rate of 5 ° C./min. The temperature was set to the point of intersection with the tangential line of the line (line after inflection) indicated by the graph after large deformation at a certain temperature.
  • Td5 ⁇ 5% mass reduction temperature (Td5)>
  • the 5% mass loss temperature (Td5) of each polymer was obtained using a differential thermal balance (“G209 F1 Libra” manufactured by NETZSCHT) under the conditions of a temperature increase rate of 10°C/min under a nitrogen atmosphere. From the obtained thermal mass curve, the temperature at which the total mass of the polymer decreased by 5% by mass was taken as the temperature. Note that Td5 is one index of heat resistance, and it can be evaluated that the larger the value, the better the heat resistance.
  • a copper foil (CF-T9DA -SV [manufactured by Fukuda Metal Foil & Powder Co., Ltd.]), pre-dried at 70° C. for 3 minutes and then at 130° C. for 3 minutes, and evaluated by visually checking for uneven coating.
  • Each polymer of Comparative Examples 1 to 9 was dissolved in N-methylpyrrolidone at a concentration shown in "Concentration of polymer solution" in Table 1, and the resulting coating film had a thickness of 20 to Apply to copper foil (CF-T9DA-SV [manufactured by Fukuda Metal Foil & Powder Co., Ltd.]) with an applicator so that it becomes 30 ⁇ m, and pre-dry at 70 ° C.
  • A There is no repelling on the copper foil, a uniform film is formed with no thickness unevenness, and a coating film that does not peel off from the copper foil is formed.
  • B Repelling occurs on the copper foil, The coating is peeling off from the copper foil and/or the coating is uneven, such as uneven thickness.
  • a copper foil (CF-T9DA- SV [manufactured by Fukuda Metal Foil & Powder Co., Ltd.]), pre-dried at 70 ° C. for 3 minutes, then at 130 ° C. for 3 minutes, further at 150 ° C. for 30 minutes, then at 250 ° C. for 3 hours, under a nitrogen atmosphere. By evaporating the solvent, a laminate composed of the polymer layer and the copper foil was obtained.
  • a solution obtained by dissolving 2 g of each polymer of Comparative Examples 1 to 9 in 8 g of N-methylpyrrolidone was applied to a copper foil (CF-T9DA-SV [Fukuda metal foil powder Kogyo Co., Ltd.]), pre-dried at 70 ° C. for 3 minutes, then at 130 ° C. for 3 minutes, and then at 150 ° C. for 30 minutes, then at 250 ° C. for 3 hours to evaporate the solvent under a nitrogen atmosphere.
  • CF-T9DA-SV Full-vinyo Co., Ltd.
  • the resulting laminate was cut into pieces of 5 mm in width and 10 cm in length, and pulled in the direction of 90 degrees at 500 mm/min using "Instron 5567" manufactured by Instron.
  • the adhesion strength between the polymer layer and the copper foil was evaluated according to the standards. When the adhesion strength was 0.2 N/mm or more, it was evaluated as "A”, and when it was less than 0.2 N/mm, it was evaluated as "B".
  • a solution obtained by dissolving 2 g of each polymer of Comparative Examples 1 to 9 in 8 g of N-methyl-2-pyrrolidone was spin-coated on a gold sputtered wafer so that the resulting coating film had a thickness of 10 to 20 ⁇ m, and the temperature was maintained at 70°C. and 5 minutes at 150° C. for 5 minutes, and then at 250° C. for 1 hour to evaporate the solvent under a nitrogen atmosphere to form a coating film.
  • a stud pin to which an epoxy resin is attached is fixed on the surface of the coating film so that the formed coating film and the epoxy resin are in contact, cured at 160 ° C. for 1 hour, and measured by a thin film adhesion strength measuring machine (manufactured by Quad Group).
  • a solution obtained by dissolving 2 g of each polymer of Comparative Examples 1 to 9 in 8 g of N-methyl-2-pyrrolidone was applied with an applicator onto a polyimide film so that the resulting coating film had a thickness of 10 to 20 ⁇ m, and the temperature was maintained at 70°C. for 5 minutes, then at 150° C. for 5 minutes, and then at 250° C. for 1 hour to evaporate the solvent under a nitrogen atmosphere to form a coated polyimide film laminate.
  • a sample is prepared by crimping a laminate in which a polyimide film with a coating film and a SUS plate are arranged so that the coating surface of each polyimide film laminate with a coating film is in contact with the SUS plate using a manual roller. bottom. Whether or not the polyimide film with the coating adhered to the SUS plate was judged by visual observation, and evaluated as "A" when adhered to the SUS plate, and as "B" when not adhered.
  • composition (I) (Example 20) Polymer (21) and cyclohexanone were placed in a glass bottle so that the solid content concentration was 30% by mass, and polymer (21) was dissolved. 16.7 g of the obtained polymer solution (amount of polymer (21): 5 g), and 5 g of 2,2-bis(4-cyanatophenyl)propane (manufactured by Tokyo Chemical Industry Co., Ltd.) as a curable compound.
  • a homogeneously mixed composition without phase separation was prepared.
  • the prepared composition is applied on a copper foil (CF-T9DA-SV [manufactured by Fukuda Metal Foil & Powder Co., Ltd.]) with a bar coater, and heated at 250 ° C. for 3 hours under nitrogen using an oven. , to obtain a copper foil with a cured product.
  • the obtained copper foil with the cured product is immersed in a 40% aqueous solution of iron (III) chloride to remove the copper foil, and the obtained cured product is washed four times with deionized water to obtain a thickness of 30 ⁇ 5 ⁇ m.
  • a film sample for evaluation was produced.
  • Example 21-33, 40-43 and Comparative Examples 20-273 A composition was prepared in the same manner as in Example 20 except that each component shown in Table 2 was used in the mass ratio shown in Table 2 (mass ratio of the polymer and the curable compound), and a film sample for evaluation was prepared. was made.
  • Example 25 and Comparative Example 23 cyanate compound A and epoxy compound D were used at a mass ratio of 50:50 as curable compounds.
  • Example 34 In a glass bottle, 16.7 g of the polymer solution of polymer (10) obtained in Example 1 (amount of polymer (10): 5 g) and 2,2-bis(4-cyanato) as a curable compound were added. 5 g of phenyl)propane (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.5 g of zinc octylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a curing aid, and an additional solvent so that the solid content concentration is 35% by mass. Cyclohexanone was added to and thoroughly stirred with a mix rotor to prepare a uniformly mixed composition without phase separation.
  • the prepared composition is applied on a copper foil (CF-T9DA-SV [manufactured by Fukuda Metal Foil & Powder Co., Ltd.]) with a bar coater, and heated at 250 ° C. for 3 hours under nitrogen using an oven. , to obtain a copper foil with a cured product.
  • the obtained copper foil with the cured product is immersed in a 40% aqueous solution of iron (III) chloride to remove the copper foil, and the obtained cured product is washed four times with deionized water to obtain a thickness of 30 ⁇ 5 ⁇ m.
  • a film sample for evaluation was produced.
  • Examples 35-39, Examples 44-49 and Examples 90-109 A composition was prepared in the same manner as in Example 34 except that each component shown in Table 2 was used in the mass ratio shown in Table 2 (mass ratio of the polymer and the curable compound), and a film sample for evaluation was prepared. was made.
  • composition (II) (Example 50) Polymer (21) and cyclohexanone were placed in a glass bottle so that the solid content concentration was 30% by mass, and polymer (21) was dissolved. 9.3 g of the resulting polymer solution (amount of polymer (21): 2.79 g), 1.2 g of ADMAFINE SC2500-SQ (manufactured by Admatechs Co., Ltd.) as a filler, and solid content as an additional solvent Cyclohexanone was added so that the concentration was 35% by mass, and the mixture was sufficiently stirred with a mix rotor to prepare a uniformly mixed composition without phase separation.
  • ADMAFINE SC2500-SQ manufactured by Admatechs Co., Ltd.
  • the prepared composition is applied on a copper foil (CF-T9DA-SV [manufactured by Fukuda Metal Foil & Powder Co., Ltd.]) with a bar coater, and heated at 250 ° C. for 3 hours under nitrogen using an oven. , to obtain a copper foil with a cured product.
  • the obtained copper foil with the cured product is immersed in a 40% aqueous solution of iron (III) chloride to remove the copper foil, and the obtained cured product is washed four times with deionized water to obtain a thickness of 30 ⁇ 5 ⁇ m.
  • a film sample for evaluation was produced.
  • Example 51-59 and Comparative Examples 30-34 A composition was prepared in the same manner as in Example 50 except that each component shown in Table 4 was used in the mass ratio shown in Table 4, and a film sample for evaluation was produced.
  • Example 60 Into a glass bottle, 9.3 g of the solution of polymer (14) obtained in Example 5 (amount of polymer (14): 2.79 g), ADMAFINE SC2500-SQ (Admatechs Co., Ltd.) as a filler ) and cyclohexanone as an additional solvent so that the solid content concentration is 35% by mass, and sufficiently stirred with a mix rotor to prepare a uniformly mixed composition without phase separation.
  • the prepared composition is applied on a copper foil (CF-T9DA-SV [manufactured by Fukuda Metal Foil & Powder Co., Ltd.]) with a bar coater, and heated at 250 ° C. for 3 hours under nitrogen using an oven.
  • CF-T9DA-SV manufactured by Fukuda Metal Foil & Powder Co., Ltd.
  • the obtained copper foil with the cured product is immersed in a 40% aqueous solution of iron (III) chloride to remove the copper foil, and the obtained cured product is washed four times with deionized water to obtain a thickness of 30 ⁇ 5 ⁇ m.
  • a film sample for evaluation was produced.
  • Example 61-72 A composition was prepared in the same manner as in Example 60, except that each component shown in Table 4 was used in the mass ratio (mass ratio of polymer and filler) shown in Table 4, to prepare a film sample for evaluation. bottom.
  • composition (III) (Example B1) Polymer (21) and cyclohexanone were put into a glass bottle so that the solid content concentration was 30% by mass, and polymer (21) was dissolved to obtain a solution of polymer (21).
  • a solution of polymer (21) (0.63 g, polymer (21) 0.19 g), and 2,2-bis(4-glycidyloxyphenyl)propane (manufactured by Tokyo Chemical Industry Co., Ltd.) as a curable compound (10.1 g) was sufficiently stirred in a glass bottle using a mix rotor to obtain a solution X.
  • the prepared composition Z is applied on a copper foil (CF-T9DA-SV [manufactured by Fukuda Metal Foil & Powder Co., Ltd.]) with a bar coater, and heated at 200 ° C. for 3 hours under nitrogen using an oven. to obtain a copper foil with a cured film.
  • the obtained copper foil with a cured film was immersed in a 40% aqueous solution of iron (III) chloride to remove the copper foil, and the obtained cured film was washed four times with deionized water to obtain a film having a thickness of 30 ⁇ 5 ⁇ m.
  • a film sample for evaluation was produced.
  • Examples B2-B3 A composition was prepared in the same manner as in Example B1 except that each component was used in the type and mass ratio (mass ratio of polymer/curable compound/reactive diluent/curing aid) shown in Table 5. Then, a film sample for evaluation was produced.
  • Example B4 A solution of polymer (39) (0.63 g) and 2,2-bis(4-glycidyloxyphenyl)propane (manufactured by Tokyo Chemical Industry Co., Ltd.) (10.1 g) as a curable compound were mixed in a glass bottle. A solution X was obtained by sufficiently stirring using a rotor. In addition, 4-methylcyclohexane-1,2-dicarboxylic anhydride (cis-, tarns-mixture) (8.9 g) as a reactive diluent and 1-benzyl-2-methylimidazole (Tokyo Chemical Industry Co., Ltd.) as a curing aid.
  • 4-methylcyclohexane-1,2-dicarboxylic anhydride cis-, tarns-mixture
  • 1-benzyl-2-methylimidazole Tokyo Chemical Industry Co., Ltd.
  • the obtained copper foil with a cured film was immersed in a 40% aqueous solution of iron (III) chloride to remove the copper foil, and the obtained cured film was washed four times with deionized water to obtain a film having a thickness of 30 ⁇ 5 ⁇ m.
  • a film sample for evaluation was produced.
  • Examples B5 to B8 A composition was prepared in the same manner as in Example B4, except that each component was used in the type and mass ratio (mass ratio of polymer/curable compound/reactive diluent/curing aid) shown in Table 5. Then, a film sample for evaluation was produced.
  • Example B9 Polymer (43) (0.26 g), 2,2-bis (4-glycidyloxyphenyl) propane (manufactured by Tokyo Chemical Industry Co., Ltd.) (4.18 g) as a curable compound, and DAW-01DC (Denka (manufactured by Co., Ltd.) (12.0 g) was sufficiently stirred in a glass bottle using a mix rotor to obtain a solution X.
  • 4-methylcyclohexane-1,2-dicarboxylic anhydride (cis-, tarns-mixture) (3.7 g) as a reactive diluent and 1-benzyl-2-methylimidazole (Tokyo Chemical Industry Co., Ltd.) as a curing aid.
  • the obtained copper foil with a cured film was immersed in a 40% aqueous solution of iron (III) chloride to remove the copper foil, and the obtained cured film was washed four times with deionized water to obtain a film having a thickness of 30 ⁇ 5 ⁇ m.
  • a film sample for evaluation was produced.
  • Example B10 A composition was prepared in the same manner as in Example B9 except that each component was used in the type and mass ratio (mass ratio of polymer / curable compound / reactive diluent / curing aid / filler) shown in Table 5. was prepared to prepare a film sample for evaluation.
  • composition (IV) (Example D1)
  • the polymer (21), a curable compound, a filler, a curing aid, and other polymers are put so that the mass ratio shown in Table 5 is obtained, and the solid content concentration is 65% by mass as an additional solvent.
  • the prepared composition is applied on a copper foil (CF-T9DA-SV [manufactured by Fukuda Metal Foil & Powder Co., Ltd.]) with a bar coater, and heated at 200 ° C. for 3 hours under nitrogen using an oven.
  • CF-T9DA-SV manufactured by Fukuda Metal Foil & Powder Co., Ltd.
  • the obtained copper foil with a cured film was immersed in a 40% aqueous solution of iron (III) chloride to remove the copper foil, and the obtained cured film was washed four times with deionized water to obtain a film having a thickness of 30 ⁇ 5 ⁇ m.
  • a film sample for evaluation was produced.
  • Example D1 except that each component shown in Table 5 was used in the mass ratio shown in Table 5 (the mass ratio of the polymer, the curable compound, the curing aid, the filler, and the other polymer) A composition was prepared in the same manner as in , and a film sample for evaluation was produced.
  • composition Appearance The appearance of the composition prepared with the composition (I) was visually observed. Each component used in the preparation of the composition was compatible, and the case where no precipitation or phase separation was observed was evaluated as "A”, and the case where precipitation or phase separation was observed was evaluated as "B”. Table 2 shows the results.
  • composition prepared from the composition (I) and composition (III) was applied to a copper foil (CF-T9DA- SV [manufactured by Fukuda Metal Foil & Powder Co., Ltd.]), pre-dried at 70 ° C. for 3 minutes, then at 130 ° C. for 3 minutes, further at 150 ° C. for 30 minutes, then at 250 ° C. for 3 hours, A cured film with a copper foil was obtained by evaporating the solvent in a nitrogen atmosphere. The obtained cured film with copper foil was immersed in 1.5 L of methyl ethyl ketone (MEK) at room temperature for 10 minutes, and then vacuum-dried at 120° C. for 3 hours.
  • MEK methyl ethyl ketone
  • Mass change rate (%) mass of cured film with copper foil after vacuum drying/mass of cured film with copper foil before immersion in MEK ⁇ 100
  • Td5 ⁇ 5% mass reduction temperature (Td5)>
  • the 5% mass loss temperature (Td5) of each evaluation film sample prepared with the composition (I) and composition (III) was measured using a differential differential thermal balance ("G209 F1 Libra" manufactured by NETZSCHT).
  • the temperature at which the total weight of the film sample for evaluation decreased by 5% by mass was taken from the thermal mass curve obtained under the conditions of a temperature increase rate of 10°C/min in a nitrogen atmosphere. The results are shown in Tables 2 and 4.
  • composition prepared in composition (I) was spin-coated on a gold sputtered wafer so that the resulting coating film had a thickness of 10 to 20 ⁇ m, and was then heated at 70° C. for 5 minutes and then at 150° C.
  • a coating film was formed by pre-drying for 5 minutes and then evaporating the solvent at 250° C. for 1 hour under a nitrogen atmosphere.
  • a stud pin to which an epoxy resin is attached is fixed on the surface of the coating film so that the formed coating film and the epoxy resin are in contact, cured at 160 ° C. for 1 hour, and measured by a thin film adhesion strength measuring machine (manufactured by Quad Group).
  • compositions prepared in the composition (I) the compositions obtained in Examples 38-39, Examples 44-45, Examples 104-106 and Comparative Examples 21-22 were added to the resulting coating film. It is applied to a copper foil (CF-T9DA-SV [manufactured by Fukuda Metal Foil & Powder Co., Ltd.]) so that the thickness is 20 to 30 ⁇ m, using an applicator, at 70 ° C. for 5 minutes, then at 150 ° C. for 5 minutes. A coating film was formed by pre-drying for 1 minute and then evaporating the solvent at 220° C. for 1 hour under a nitrogen atmosphere.
  • CF-T9DA-SV manufactured by Fukuda Metal Foil & Powder Co., Ltd.
  • a 50 ⁇ m-thick polyimide film manufactured by Toray DuPont Co., Ltd., “Kapton 200H” was applied with a resin manual roller at room temperature (Examples 38-39, Examples 44-45 , Examples 104 to 105) or 80° C. (Example 106, Comparative Examples 21 and 22) to prepare samples.
  • the adhesiveness was evaluated by peeling the polyimide film from the prepared sample. It was evaluated as "A" when it had adhesiveness due to lamination, that is, when it was sticky and could be temporarily adhered like an adhesive tape, and when it was peeled off because it was not adhesive and could not be temporarily adhered. Table 3 shows the results.
  • the resulting laminate was cut into pieces of 5 mm in width and 10 cm in length, and pulled in the direction of 90 degrees under conditions of 500 mm/min using "Instron 5567" manufactured by Instron. was evaluated for adhesion strength between the polymer layer and the copper foil. When the adhesion strength was 0.2 N/mm or more, it was evaluated as "A”, and when it was less than 0.2 N/mm, it was evaluated as "B".
  • Reactive diluent > - Reactive diluent A: 4-methylcyclohexane-1,2-dicarboxylic anhydride (cis-, tarns-mixture) (manufactured by Tokyo Chemical Industry Co., Ltd.) - Reactive diluent B: o-cresyl glycidyl ether (manufactured by Yokkaichi Gosei Co., Ltd.)
  • the polymer has excellent heat resistance, is soluble in general-purpose solvents, and has excellent applicability and adhesion to substrates such as copper substrates and gold substrates.
  • the present composition obtained by appropriately combining the present polymer with various curable compounds, fillers, etc., it has excellent heat resistance, and has excellent applicability and adhesion to substrates such as copper substrates and gold substrates.
  • a cured product (cured product layer) having excellent properties can be formed. Therefore, the present polymer and the present composition can be suitably used in a wide range of fields such as structural materials used in the transportation industry such as the aircraft industry and automobile industry, and electrical and electronic materials used in the electrical and electronic industry.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
PCT/JP2023/002850 2022-02-01 2023-01-30 重合体、組成物、硬化物、積層体および電子部品 Ceased WO2023149394A1 (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2023578543A JPWO2023149394A1 (https=) 2022-02-01 2023-01-30
EP23749710.2A EP4474427A4 (en) 2022-02-01 2023-01-30 POLYMER, COMPOSITION, HARDENED PRODUCT, MULTILAYER BODY AND ELECTRONIC COMPONENT
KR1020247020563A KR20240136937A (ko) 2022-02-01 2023-01-30 중합체, 조성물, 경화물, 적층체 및 전자 부품
CN202380015052.3A CN118401610A (zh) 2022-02-01 2023-01-30 聚合物、组合物、硬化物、层叠体和电子零件
US18/834,042 US20250122404A1 (en) 2022-02-01 2023-01-30 Polymer, composition, cured product, laminated body, and electronic component

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022-013985 2022-02-01
JP2022013985 2022-02-01

Publications (1)

Publication Number Publication Date
WO2023149394A1 true WO2023149394A1 (ja) 2023-08-10

Family

ID=87552334

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/002850 Ceased WO2023149394A1 (ja) 2022-02-01 2023-01-30 重合体、組成物、硬化物、積層体および電子部品

Country Status (7)

Country Link
US (1) US20250122404A1 (https=)
EP (1) EP4474427A4 (https=)
JP (1) JPWO2023149394A1 (https=)
KR (1) KR20240136937A (https=)
CN (1) CN118401610A (https=)
TW (1) TW202337952A (https=)
WO (1) WO2023149394A1 (https=)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024210079A1 (ja) * 2023-04-03 2024-10-10 ナミックス株式会社 新規アクリルアミド、それを含む組成物、硬化性組成物、接着剤、封止材、硬化物、半導体装置及び電子部品
WO2025229988A1 (ja) * 2024-05-02 2025-11-06 日産化学株式会社 無溶剤型組成物及び硬化膜
WO2026074858A1 (ja) * 2024-10-01 2026-04-09 ナミックス株式会社 新規（メタ）アクリルアミド、それを含む組成物、硬化性組成物、接着剤、封止材、硬化物、半導体装置及び電子部品

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120829715A (zh) * 2025-09-16 2025-10-24 陕西至强重防材料技术有限公司 一种燃料电池水冷板绝缘涂层材料及其制备方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02232230A (ja) * 1989-01-24 1990-09-14 Himont It Srl トリアジンポリマーの調製方法
JPH0912712A (ja) 1995-06-27 1997-01-14 Lion Corp ダイマージアミン由来のポリアミド樹脂及び該ポリアミドを含有する合成樹脂製光学用材料
JPH11129399A (ja) 1997-10-31 1999-05-18 Nippon Zeon Co Ltd 複合フィルム
WO2001097582A1 (en) 2000-06-15 2001-12-20 Ajinomoto Co., Inc. Adhesive film and method for manufacturing multilayer printed wiring board comprising the same
WO2005025857A1 (ja) 2003-09-10 2005-03-24 Zeon Corporation 樹脂複合フィルム
JP2006178059A (ja) 2004-12-21 2006-07-06 Hitachi Chemical Dupont Microsystems Ltd ネガ型感光性樹脂組成物、パターンの製造方法及び電子部品
JP2012226297A (ja) 2011-04-08 2012-11-15 Dainippon Printing Co Ltd レジスト帯電防止膜積層体、レリーフパターン製造方法及び電子部品
JP2013155329A (ja) * 2012-01-31 2013-08-15 T & K Toka Co Ltd 溶剤可溶性ポリイミド樹脂及びその製造方法、並びに前記ポリイミド樹脂を含有するポリイミド組成物、ポリイミドフィルム、及びコーティング物品
JP2014186300A (ja) 2013-02-21 2014-10-02 Jsr Corp 感光性組成物、硬化膜およびその製造方法ならびに電子部品

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02232230A (ja) * 1989-01-24 1990-09-14 Himont It Srl トリアジンポリマーの調製方法
JPH0912712A (ja) 1995-06-27 1997-01-14 Lion Corp ダイマージアミン由来のポリアミド樹脂及び該ポリアミドを含有する合成樹脂製光学用材料
JPH11129399A (ja) 1997-10-31 1999-05-18 Nippon Zeon Co Ltd 複合フィルム
WO2001097582A1 (en) 2000-06-15 2001-12-20 Ajinomoto Co., Inc. Adhesive film and method for manufacturing multilayer printed wiring board comprising the same
WO2005025857A1 (ja) 2003-09-10 2005-03-24 Zeon Corporation 樹脂複合フィルム
JP2006178059A (ja) 2004-12-21 2006-07-06 Hitachi Chemical Dupont Microsystems Ltd ネガ型感光性樹脂組成物、パターンの製造方法及び電子部品
JP2012226297A (ja) 2011-04-08 2012-11-15 Dainippon Printing Co Ltd レジスト帯電防止膜積層体、レリーフパターン製造方法及び電子部品
JP2013155329A (ja) * 2012-01-31 2013-08-15 T & K Toka Co Ltd 溶剤可溶性ポリイミド樹脂及びその製造方法、並びに前記ポリイミド樹脂を含有するポリイミド組成物、ポリイミドフィルム、及びコーティング物品
JP2014186300A (ja) 2013-02-21 2014-10-02 Jsr Corp 感光性組成物、硬化膜およびその製造方法ならびに電子部品

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
MACROMOLECULES, vol. 2003, no. 36, pages 8320 - 8329
MACROMOLECULES, vol. 3, 1970, pages 533 - 535
See also references of EP4474427A4

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024210079A1 (ja) * 2023-04-03 2024-10-10 ナミックス株式会社 新規アクリルアミド、それを含む組成物、硬化性組成物、接着剤、封止材、硬化物、半導体装置及び電子部品
WO2025229988A1 (ja) * 2024-05-02 2025-11-06 日産化学株式会社 無溶剤型組成物及び硬化膜
WO2026074858A1 (ja) * 2024-10-01 2026-04-09 ナミックス株式会社 新規（メタ）アクリルアミド、それを含む組成物、硬化性組成物、接着剤、封止材、硬化物、半導体装置及び電子部品

Also Published As

Publication number Publication date
US20250122404A1 (en) 2025-04-17
KR20240136937A (ko) 2024-09-19
EP4474427A1 (en) 2024-12-11
TW202337952A (zh) 2023-10-01
EP4474427A4 (en) 2025-12-31
CN118401610A (zh) 2024-07-26
JPWO2023149394A1 (https=) 2023-08-10

Similar Documents

Publication Publication Date Title
US12247104B2 (en) Polyamic acid resin, polyimide resin, and resin composition including these
WO2023149394A1 (ja) 重合体、組成物、硬化物、積層体および電子部品
CN109071804B (zh) 聚合物、组合物、成形体、硬化物以及层叠体
TW575636B (en) Heat-resistant composition
EP2159247B1 (en) Solvent-free polymide silicone resin compositions and cured products thereof
JP5499544B2 (ja) 熱硬化性絶縁樹脂組成物、並びにこれを用いたプリプレグ、樹脂付フィルム、積層板、及び多層プリント配線板
TWI424006B (zh) 熱硬化性聚醯亞胺矽樹脂組成物及其硬化皮膜
TW201105632A (en) Thermosetting resin composition, and prepreg, insulating film with support, laminate plate, and printed wiring board, each obtained using same
JP7147940B2 (ja) 組成物、硬化物及び積層体
JP5521853B2 (ja) アンダーフィル剤およびそれを用いた半導体装置
JP2020105493A (ja) ポリイミド、ポリイミド樹脂組成物、ポリイミドフィルム、接着剤、フィルム状接着材、接着層、接着シート、樹脂付銅箔、銅張積層板及びプリント配線板、並びに、ポリイミドの製造方法
JP2010043254A (ja) 熱硬化性絶縁樹脂組成物、並びにこれを用いたプリプレグ、樹脂付フィルム、積層板、及び多層プリント配線板
CN106084184A (zh) 组合物、环氧树脂固化剂、环氧树脂组合物、热固性组合物、固化物、半导体装置以及层间绝缘材料
JP2022077849A (ja) 熱硬化性マレイミド樹脂組成物、並びにその樹脂組成物からなる未硬化樹脂フィルム及び硬化樹脂フィルム
TWI432487B (zh) Flammable polyimide silicone resin composition
TWI911327B (zh) 樹脂組成物
TWI841750B (zh) 芳香族雙馬來醯亞胺化合物及其製造方法、以及含有該化合物的熱硬化性環狀醯亞胺樹脂組合物
JP2022122748A (ja) 樹脂組成物
JP7144182B2 (ja) 硬化性樹脂組成物、硬化物、接着剤、及び、接着フィルム
TW202233731A (zh) 樹脂組成物、片狀組成物、片硬化物、積層體、積層構件、晶圓保持體及半導體製造裝置
JP7342962B2 (ja) 組成物、硬化物、積層体及び電子部品
TW202535659A (zh) 附有金屬箔之樹脂薄片
TW202539893A (zh) 附有金屬箔之樹脂薄片
TW202602693A (zh) 半導體封裝基板的絕緣層形成用的樹脂片材
TW202603050A (zh) 樹脂組成物

Legal Events

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

Ref document number: 23749710

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 202380015052.3

Country of ref document: CN

ENP Entry into the national phase

Ref document number: 2023578543

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 18834042

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 2023749710

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2023749710

Country of ref document: EP

Effective date: 20240902

WWP Wipo information: published in national office

Ref document number: 18834042

Country of ref document: US