TW202323323A - Copolymer and resin composition - Google Patents

Abstract

The purpose of the present disclosure is to provide a copolymer having excellent solvent solubility and low dielectric loss tangent. This copolymer includes: an aromatic vinyl monomer unit; a crosslinkable group-containing monomer unit; and a monomer unit from which a homopolymer having a glass transition temperature of 150 DEG C or higher is obtained.

Description

Copolymer, and resin composition

The present invention relates to a copolymer and a resin composition.

In recent years, electrical equipment, electronic equipment, and communication equipment have been developing at an astonishing speed. Currently, there is a tendency for these machines to use higher frequency bands. Typically, these machines use various printed substrates. Therefore, excellent electrical characteristics corresponding to high-frequency band frequencies, excellent heat resistance to the extent that it can withstand soldering work, and the like are also required for printed circuit boards.

For example, Patent Document 1 discloses an invention related to a composition comprising a specific fluorine-containing thermosetting resin, a silicone compound, and a catalyst for hydrosilylation reaction. However, the specifically disclosed fluorine-containing thermosetting resins are obtained by introducing crosslinking groups into OH-group-containing fluorine resins through polymer reactions.

Patent Document 2 discloses an invention related to a specific laminate, and describes the use of a fluorine-containing thermosetting resin to introduce a crosslinking group. However, it merely describes the introduction of a crosslinking group, etc., into an OH group-containing fluororesin by polymer reaction.

Patent Document 3 discloses an invention related to a specific curable resin composition composed of a fluorine-containing polymer and a hydrosilylation crosslinking agent, and exemplifies dicyclopentadiene and fluoroolefins. However, the polymerization efficiency cannot be said to be good. Also, a curing system using a crosslinking agent in combination is disclosed, but a curing reaction performed only by heat is not disclosed. [Prior Art Literature] [Patent Document]

[Patent Document 1] International Publication No. 2008/044765 [Patent Document 2] Japanese Unexamined Patent Publication No. 2014-26619 [Patent Document 3] International Publication No. 2011/115042

[Problem to be Solved by the Invention]

The invention provides a copolymer with excellent solvent solubility and low dielectric loss tangent. [Technical means to solve the problem]

The present invention (1) relates to a copolymer comprising an aromatic vinyl monomer unit, a crosslinking group-containing monomer unit, and a monomer unit providing a homopolymer having a glass transition temperature of 150° C. or higher.

The present invention (2) is the copolymer of the present invention (1), which is a thermosetting resin.

The present invention (3) is the copolymer according to the present invention (1) or (2), wherein the aromatic vinyl monomer unit is a styrene unit.

The present invention (4) is a copolymer optionally combined with any one of the present inventions (1) to (3), wherein the monomer unit containing a crosslinking group includes a diene monomer unit having an alicyclic structure .

The present invention (5) is a copolymer arbitrarily combined with any one of the present inventions (1) to (3), wherein the monomer unit containing a crosslinking group includes a monomer unit having a dicyclopentenyl structure .

The present invention (6) is a copolymer arbitrarily combined with any one of the present inventions (1) to (3), wherein the above-mentioned monomer unit containing a crosslinking group comprises a dicyclopentadiene unit and a dicyclopentadiene unit. At least one of the group consisting of pentenyl vinyl ether units.

The present invention (7) is a copolymer in any combination with any one of the present inventions (1) to (6), wherein the above-mentioned monomer unit providing a homopolymer with a glass transition temperature of 150°C or higher contains maleic acid imine unit.

The present invention (8) is a copolymer according to the present invention (7), wherein the above-mentioned maleimide unit comprises a unit selected from N-cyclohexylmaleimide unit and N-phenylmaleimide unit at least one of the group formed.

The present invention (9) is a copolymer optionally combined with any one of the present inventions (1) to (8), which further comprises a fluorine-containing monomer unit providing a C-F bond to the main chain.

The present invention (10) is a copolymer optionally combined with any one of the present inventions (1) to (9), and has a glass transition temperature of 140°C or higher.

The present invention (11) is a copolymer which is optionally combined with any one of the present inventions (2) to (10), and has a thermosetting temperature of 240°C or lower.

The present invention (12) is a copolymer optionally combined with any one of the present inventions (1) to (11), which has solubility in methyl ethyl ketone or toluene.

The present invention (13) is a copolymer arbitrarily combined with any one of the present inventions (1) to (12), wherein, relative to all polymerized units constituting the above-mentioned copolymer, the above-mentioned crosslinking group-containing monomer unit is More than 1 mol%.

The present invention (14) is a copolymer optionally combined with any one of the present inventions (1) to (13), wherein, relative to all polymerized units constituting the above-mentioned copolymer, the above-mentioned provided glass transition temperature is 150°C or higher. The monomer unit of the homopolymer is more than 5 mol%.

The present invention (15) is a copolymer which is optionally combined with any one of the present inventions (1) to (14), and has a dielectric loss tangent of 0.0030 or less.

The present invention (16) relates to a copolymer composition comprising a copolymer optionally combined with any one of the present inventions (1) to (15), and a solvent.

The present invention (17) is the copolymer composition of the present invention (16), which contains a polymer containing a plurality of vinyl groups or a monomer component containing a plurality of vinyl groups.

The present invention (18) is the copolymer composition according to the present invention (16) or (17), which contains a photopolymerization initiator.

The present invention (19) is a copolymer composition which is optionally combined with any one of the present inventions (16) to (18), and has a gel fraction of 30% or more.

The present invention (20) relates to a film comprising a copolymer arbitrarily combined with any one of the present inventions (1) to (15).

The present invention (21) relates to a laminate comprising a base material and a resin layer provided on the base material, and the resin layer includes a copolymerized product in any combination with any one of the present inventions (1) to (15). thing.

The present invention (22) relates to a metal-clad laminate comprising a metal foil and a resin layer provided on the metal foil, and the resin layer includes any one of the present inventions (1) to (15). Combination of copolymers.

The present invention (23) relates to a printed circuit board characterized by comprising a pattern circuit formed by etching the metal foil of the metal-clad laminate of the present invention (22). [Effect of Invention]

According to the present invention, it is possible to provide a copolymer excellent in solvent solubility and low dielectric loss tangent.

As described in Patent Documents 1, 2, etc., it is generally necessary to introduce a crosslinking group to make the resin (polymer) a thermosetting resin. Moreover, the introduction of the crosslinking group usually adopts the method of synthesizing polymers containing OH groups and introducing acryl groups through polymer reactions, especially by reacting acrylic monomers with isocyanate groups with OH groups to introduce them. The method is relatively simple and often used. However, the electrical properties of resins with acryl groups as crosslinking groups are not so good. As another method, there is also a method of simply copolymerizing a diene monomer during polymerization, but there is a problem that gelation occurs during polymerization or the amount of crosslinking groups introduced is limited.

The present inventors have worked hard to study and found that by using the aromatic vinyl monomers of the present invention, monomers containing crosslinking groups, and copolymers (resins) of monomers that provide homopolymers with a glass transition temperature of 150° C. or more ), can provide a copolymer with excellent solvent solubility and low dielectric loss tangent, thereby completing the present invention.

The copolymer (resin) of the present invention has an aromatic vinyl monomer unit, a monomer unit containing a crosslinking group, and a monomer unit providing a homopolymer with a glass transition temperature of 150°C or higher. By having these three types of units, the above-mentioned copolymer is endowed with a very low dielectric loss tangent, and is also excellent in solvent solubility. In addition, the dielectric constant and linear expansion rate are also low. Furthermore, since a monomer unit containing a crosslinking group is introduced, self-crosslinking (thermal crosslinking, etc.) is possible without particularly using a crosslinking agent, and good thermosetting properties can also be imparted.

The copolymer of the present invention has an aromatic vinyl monomer unit. "Aromatic vinyl monomer unit" is a polymerized unit based on an aromatic vinyl monomer. The above-mentioned copolymer may contain one type of aromatic vinyl monomer unit, or may contain two or more types of aromatic vinyl monomer units. Furthermore, the above-mentioned aromatic vinyl monomer unit may be any one of a fluorine-containing monomer unit (a polymerized unit based on a fluorine-containing monomer) and a fluorine-free monomer unit (a polymerized unit based on a fluorine-free monomer). .

The above-mentioned aromatic vinyl monomer system includes monomers containing an aromatic ring and a vinyl group in the molecule, for example, styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, Tributyl styrene, etc. Among the above-mentioned aromatic vinyl monomer units, styrene units are preferred from the viewpoint of low dielectric constant and low dielectric loss tangent.

Regarding the above-mentioned aromatic vinyl monomer unit, based on the aspect of excellent low dielectric constant and low dielectric loss tangent, it is preferably 5 mol% or more, more preferably 20 mol % or more, more preferably 30 mol % or more, and more preferably 90 mol % or less, more preferably 80 mol % or less, further preferably 70 mol % or less.

The copolymer of the present invention has a monomer unit containing a crosslinking group. The "crosslinking group-containing monomer unit" is a polymerized unit based on a crosslinking group-containing monomer (monomer having a crosslinking group). The above-mentioned copolymer may contain one type of crosslinking group-containing monomer unit, or may contain two or more types of crosslinking group-containing monomer units. Furthermore, the above-mentioned crosslinking group-containing monomer unit may be either a fluorine-containing monomer unit or a fluorine-free monomer unit.

The above-mentioned cross-linking group-containing monomer is a monomer containing a cross-linking group (group having cross-linking property) in the molecule. The crosslinking group may, for example, be a group containing a carbon-carbon double bond, a halogen atom, an acid anhydride group, a carboxyl group, an amino group, a cyano group, or a hydroxyl group.

Regarding the above-mentioned monomer units containing crosslinking groups, based on the excellent aspects of low dielectric constant and low dielectric loss tangent, it is preferably 1 mol% or more, more preferably It is 3 mol% or more, more preferably 5 mol% or more, and is preferably 50 mol% or less, more preferably 30 mol% or less, still more preferably 20 mol% or less.

The above-mentioned monomer unit containing a crosslinking group is not particularly limited as long as it is a monomer unit having a crosslinking group. Based on the viewpoint of low dielectric constant and low dielectric loss tangent, it is preferred to have an alicyclic Structured diene monomer units (polymerized units based on diene monomers having an alicyclic structure).

As for the above-mentioned diene monomer having an alicyclic structure, for example, a monocyclic alicyclic diene, a polycyclic alicyclic condensed diene, and a crosslinked cyclodiene may be mentioned. Examples of monocyclic alicyclic dienes include: 1,4-cyclohexadiene, 1,5-cyclooctadiene, 1,5-cyclododecane, 4-vinylcyclohexene, 1-allyl-4-isopropylidenecyclohexane, 3-allylcyclopentene, 1-isopropenyl-4-(4-butenyl)cyclohexane, limonene and the like. Examples of polycyclic alicyclic condensed dienes and crosslinked cyclodienes include tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, bicyclo(2,2,1)hept-2, 5-diene, 2-methylbicycloheptadiene, or alkenyl, alkylene, cycloalkenyl and cycloalkylene norbornene (5-methylene-2-norbornene, 5-methylene ethyl-2-norcamphene, 5-isopropylidene norcamphene, 5-(4-cyclopentenyl)-2-norcamphene, 5-cyclohexylene-2-norcamphene, etc.). Among them, limonene, dicyclopentadiene, and 5-ethylidene-2-norcamphene are preferred.

As the above-mentioned crosslinking group-containing monomer unit, from the viewpoint of low dielectric constant and low dielectric loss tangent, it is also preferably selected from dicyclopentadiene units (polymerized units based on dicyclopentadiene) and at least one of the group consisting of monomer units having a dicyclopentenyl structure (polymerized units based on monomers having a dicyclopentenyl structure). Among them, a monomer unit having a dicyclopentenyl structure is more preferable. Here, the monomer unit having a dicyclopentenyl structure preferably contains 0 to 1 heteroatom.

Among the above-mentioned crosslinking group-containing monomer units, preferably at least one selected from the group consisting of dicyclopentadiene units and dicyclopentenyl vinyl ether units.

The aforementioned dicyclopentadiene (DCPD) is a monomer represented by the following formula.

Regarding the above-mentioned dicyclopentadiene unit, based on the excellent aspect of low dielectric constant and low dielectric loss tangent, it is preferably at least 1 mole %, more preferably 3 Mole % or more, more preferably 5 Mole % or more, and more preferably 50 Mole % or less, more preferably 30 Mole % or less, further preferably 20 Mole % or less.

As a monomer containing the said dicyclopentenyl structure, the monomer etc. which have the dicyclopentenyl group represented by following formula (I-1) and (I-2) are mentioned, for example.

（式中，R ⁵¹為氫原子或甲基）。 The following compounds etc. are mentioned as a monomer which has the dicyclopentenyl group represented by said formula (I-1) and (I-2).

(In the formula, R ⁵¹ is a hydrogen atom or a methyl group).

Among them, compounds represented by the following formulas are preferred.

As a specific example of the monomer which has the dicyclopentenyl group represented by said formula (I-1) and (I-2), dicyclopentenyl acrylate, dicyclopentenyl methacrylate, etc. are illustrated.

（式中，R ⁶¹為氫原子或甲基）。 The following compounds etc. are also mentioned as a monomer which has the dicyclopentenyl group represented by said formula (I-1) and (I-2).

(In the formula, R ⁶¹ is a hydrogen atom or a methyl group).

Among them, compounds represented by the following formulas are preferred.

As a specific example of the monomer having the dicyclopentenyl group represented by said formula (I-1) and (I-2), dicyclopentenyl vinyl ether etc. can be illustrated.

Regarding the above-mentioned monomer units containing a dicyclopentenyl structure, based on the excellent aspects of low dielectric constant and low dielectric loss tangent, it is preferably 1 mol% or more relative to all polymerized units constituting the above-mentioned copolymer , more preferably at least 3 mol%, more preferably at least 5 mol%, and more preferably at most 50 mol%, more preferably at most 30 mol%, further preferably at most 20 mol%.

The copolymer of the present invention has the above-mentioned monomer unit providing a homopolymer having a glass transition temperature (Tg) of 150°C or higher (based on the polymerized unit of a monomer providing a homopolymer having a Tg of 150°C or higher). "Monomer unit providing a homopolymer having a glass transition temperature of 150°C or higher" is a polymerized unit based on the following monomer in the case of producing a homopolymer obtained by polymerizing only the same type of monomer , The glass transition temperature is above 150°C. The above-mentioned copolymer may contain one type of such monomer units, or may contain two or more types of such monomer units. Furthermore, the monomer unit may be either a fluorine-containing monomer unit or a fluorine-free monomer unit.

With regard to the above-mentioned monomer unit providing a homopolymer having a glass transition temperature (Tg) of 150°C or higher, the Tg is preferably 170°C or higher, more preferably 200°C or higher, further preferably 250°C or higher, and more preferably It is 400°C or lower, more preferably 350°C or lower, still more preferably 320°C or lower. The above Tg is a value measured by a differential scanning calorimeter (DSC).

With regard to the above-mentioned monomer units for providing a homopolymer having a glass transition temperature of 150° C. or higher, based on the aspect of excellent low dielectric constant and low dielectric loss tangent, relative to all the polymerized units constituting the above-mentioned copolymer, preferably 5 mol% or more, more preferably 20 mol% or more, more preferably 30 mol% or more, and preferably 80 mol% or less, more preferably 70 mol% or less, and more preferably 60 mol% Ear % below.

As the above-mentioned monomer unit for providing a homopolymer having a glass transition temperature of 150° C. or higher, based on the excellent aspects of low dielectric constant and low dielectric loss tangent, it is preferable to include maleimide units (maleimide based Monomer units based on N-substituted maleimides), more preferably N-substituted maleimides (based on monomer units based on N-substituted maleimides). Among them, it is more desirable to contain monomer units represented by the following formulas (II-1) and (II-2).

（式中，R ¹¹為碳數7～14之芳基烷基、或碳數6～14之芳基。R ¹²及R ¹³分別獨立地為氫原子、氧原子、硫原子、碳數1～12之烷基、或碳數6～14之芳基。再者，R ¹¹、R ¹²、R ¹³亦可具有取代基）。

(In the formula, R ¹¹ is an arylalkyl group with 7 to 14 carbons, or an aryl group with 6 to 14 carbons. ^{R 12} and R ¹³ are independently a hydrogen atom, an oxygen atom, a sulfur atom, or an aryl group with 1 to 14 carbons. 12 alkyl groups, or aryl groups having 6 to 14 carbon atoms. Furthermore, R ¹¹ , R ¹² , and R ¹³ may have substituents).

（式中，R ¹⁴為氫原子、碳數3～12之環烷基、或碳數1～12之烷基。R ¹⁵及R ¹⁶分別獨立地為氫原子、氧原子、硫原子、碳數1～12之烷基、或碳數6～14之芳基。再者，R ¹⁴、R ¹⁵、R ¹⁶亦可具有取代基）。

(In the formula, R ¹⁴ is a hydrogen atom, a cycloalkyl group with 3 to 12 carbons, or an alkyl group with 1 to 12 carbons. ^{R 15} and R ¹⁶ are independently hydrogen atom, oxygen atom, sulfur atom, carbon number an alkyl group with 1 to 12 carbon atoms, or an aryl group with 6 to 14 carbon atoms. Furthermore, R ¹⁴ , R ¹⁵ , and R ¹⁶ may have substituents).

Examples of substituents in R ¹¹ to R ¹⁶ of the above formulas (II-1) and (II-2) include: halogen atoms, alkyl groups having 1 to 6 carbon atoms, and alkoxy groups having 1 to 6 carbon atoms , nitro, benzyl, etc.

Examples of the monomer forming the monomer unit represented by the above formula (II-1) include N-arylmaleimides, N-aromatic substituted maleimides, and the like. Specifically, N-phenylmaleimide, N-benzylmaleimide, N-(2-chlorophenyl)maleimide, N-(4-chlorobenzene base)maleimide, N-(4-bromophenyl)maleimide, N-(2-methylphenyl)maleimide, N-(2,6-dimethylbenzene base)maleimide, N-(2-ethylphenyl)maleimide, N-(2-methoxyphenyl)maleimide, N-(2-nitrophenyl )maleimide, N-(2,4,6-trimethylphenyl)maleimide, N-(4-benzylphenyl)maleimide, N-(2,4 ,6-tribromophenyl)maleimide, N-naphthylmaleimide, N-anthracenylmaleimide, 3-methyl-1-phenyl-1H-pyrrole-2, 5-diketone, 3,4-dimethyl-1-phenyl-1H-pyrrole-2,5-dione, 1,3-diphenyl-1H-pyrrole-2,5-dione, 1, 3,4-triphenyl-1H-pyrrole-2,5-dione, etc. Among them, based on the viewpoint of low dielectric constant and low dielectric loss tangent, N-phenylmaleimide and N-benzylmaleimide are preferred, and N-phenylmaleimide is more preferred. imide.

Regarding the monomer unit represented by the above formula (II-1), based on the excellent low dielectric constant and low dielectric loss tangent, it is preferably 5 mol% relative to all the polymerized units constituting the above copolymer Above, more preferably at least 20 mol%, more preferably at least 30 mol%, and more preferably at most 80 mol%, more preferably at most 70 mol%, further preferably at most 60 mol%.

As a monomer forming the monomer unit represented by the above formula (II-2), for example, N-methylmaleimide, N-ethylmaleimide, N-n-propylmaleimide Laimide, N-isopropylmaleimide, N-n-butylmaleimide, N-isobutylmaleimide, N-second butylmaleimide, N-tert-butylmaleimide, N-pentylmaleimide, N-hexylmaleimide, N-heptylmaleimide, N-octylmaleimide N-laurylmaleimide, N-laurylmaleimide, N-2-ethylhexylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N -Cyclohexylmethylmaleimide, 1-cyclohexyl-3-methyl-1H-pyrrole-2,5-dione, 1-cyclohexyl-3,4-dimethyl-1H-pyrrole-2 ,5-Diketone, 1-cyclohexyl-3-phenyl-1H-pyrrole-2,5-dione, 1-cyclohexyl-3,4-diphenyl-1H-pyrrole-2,5-dione wait. Among them, based on the viewpoint of low dielectric constant and low dielectric loss tangent, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide are preferred. Amine, N-cyclohexylmaleimide, more preferably N-cyclohexylmaleimide.

Regarding the monomer unit represented by the above formula (II-2), based on the excellent aspect of low dielectric constant and low dielectric loss tangent, it is preferably 5 mol% relative to all the polymerized units constituting the above copolymer Above, more preferably at least 20 mol%, more preferably at least 30 mol%, and more preferably at most 80 mol%, more preferably at most 70 mol%, further preferably at most 60 mol%.

Regarding the total unit amount of the monomer units represented by the above formulas (II-1) and (II-2), based on the excellent low dielectric constant and low dielectric loss tangent, relative to the total amount of the copolymer constituting the above-mentioned The polymerized unit is preferably at least 5 mol%, more preferably at least 20 mol%, more preferably at least 30 mol%, and preferably less than 80 mol%, more preferably less than 70 mol%, Furthermore, it is more preferably 60 mol% or less.

The above-mentioned maleimide-based unit preferably includes at least one selected from the group consisting of N-cyclohexylmaleimide units and N-phenylmaleimide units.

Regarding the copolymer of the present invention, based on the viewpoint of low dielectric constant and low dielectric loss tangent, the "mole ratio of aromatic vinyl monomer unit/crosslinking group-containing monomer unit" is preferably (50 -95)/(5-50), more preferably (55-95)/(5-45), still more preferably (60-95)/(5-40).

Regarding the copolymer of the present invention, based on the viewpoint of low dielectric constant and low dielectric loss tangent, "providing the monomer unit of the homopolymer with a glass transition temperature of 150°C or higher/crosslinking group-containing monomer unit The "molar ratio" is preferably (50-95)/(5-50), more preferably (60-90)/(10-40), still more preferably (65-90)/(10-35).

In the above-mentioned copolymer, with respect to all the polymerized units, the above-mentioned aromatic vinyl monomer unit, the above-mentioned crosslinking group-containing monomer unit, and the above-mentioned monomer unit providing a homopolymer having a glass transition temperature of 150°C or higher The total content is preferably at least 70 mol%, more preferably at least 80 mol%, even more preferably at least 90 mol%, even more preferably at least 95 mol%, especially preferably at least 97 mol%. It may be 100 mol% with respect to all polymerized units.

Regarding the copolymer of the present invention, based on the viewpoint of low dielectric constant and low dielectric loss tangent, it is preferable to further have a fluorine-containing monomer unit (hereinafter, also referred to as "fluorine-containing unit) that provides a C-F bond to the main chain. body unit"). In this case, the above-mentioned copolymer contains fluorine atoms and has C-F bonds between carbon atoms forming the main chain and fluorine atoms.

The above-mentioned fluorine-containing monomer units (polymerized units based on fluorine-containing monomers) can be introduced into the copolymer by using fluorine-containing monomers. The above-mentioned fluorine-containing monomer may be either a cyclic monomer or an acyclic monomer. Cyclic monomers and acyclic monomers preferably have C-F bonds between carbon atoms and fluorine atoms forming the main chain of the copolymer.

Examples of the above-mentioned fluorine-containing monomers include fluorine-containing vinyl monomers, fluorine-containing acrylic monomers, fluorine-containing styrene monomers, hydrofluoroolefins, fluorine-containing norbornene, and the like. Among them, fluorine-containing vinyl monomers and fluorine-containing acrylic monomers are preferred.

As the above-mentioned fluorine-containing vinyl monomer, it is preferably selected from the group consisting of tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP) and perfluoro(alkyl vinyl ether). At least one, more preferably at least one selected from the group consisting of TFE, CTFE, HFP and perfluoro(alkyl vinyl ether). Based on having a low dielectric constant and a low dielectric loss tangent and having excellent dispersibility, moisture resistance, heat resistance, flame retardancy, adhesiveness, and chemical resistance, etc., and based on having a low dielectric constant In terms of low dielectric loss tangent and excellent weather resistance and moisture resistance, it is more preferably at least one selected from the group consisting of TFE, CTFE and HFP, based on the aspect of not containing chlorine, and further preferred At least one selected from the group consisting of TFE and HFP is preferable, and TFE is particularly preferable in terms of excellent copolymerizability. Examples of the above-mentioned perfluoro(alkyl vinyl ether) include: perfluoro(methyl vinyl ether) (PMVE), perfluoro(ethyl vinyl ether) (PEVE), perfluoro(propyl vinyl ether) ) (PPVE), perfluoro(butyl vinyl ether), etc., but not limited to them.

Among the above-mentioned fluorine-containing vinyl monomers, preferably fluorine-containing ethylene, fluorine-containing propylene, fluorine-containing vinyl ether, etc., more preferably tetrafluoroethylene, trifluorochloroethylene, hexafluoropropylene, perfluoro(alkylethylene) base ether).

（式中，R ⁷¹～R ⁷⁴相互獨立地為1價基，R ⁷¹～R ⁷³之至少一者為氟原子或CF ₃基）。 Especially preferred is a fluorine-containing vinyl monomer represented by the following formula.

(In the formula, R ⁷¹ to R ⁷⁴ are independently monovalent groups, and at least one of R ⁷¹ to R ⁷³ is a fluorine atom or a CF ₃ group).

The monovalent groups as R ⁷¹ to R ⁷⁴ include, for example, a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, etc.), a monovalent hydrocarbon group, and the like. The said monovalent hydrocarbon group may have heteroatoms, such as a nitrogen atom and an oxygen atom. The above-mentioned monovalent hydrocarbon group may be any of linear, branched and cyclic. The carbon number of the said monovalent hydrocarbon group becomes like this. Preferably it is 1-8, More preferably, it is 1-5, More preferably, it is 1-3. As said monovalent hydrocarbon group, an alkyl group, an alkenyl group, an alkynyl group etc. which have the said carbon number are mentioned. The monovalent group is preferably a hydrogen atom, a fluorine atom, a chlorine atom, a fluorinated alkyl group with the above-mentioned carbon number, or a fluorinated alkoxy group with the above-mentioned carbon number.

（式中，R ⁴¹表示可經1個以上之氟原子取代之烷基）。 As the above-mentioned fluorine-containing acrylic monomer, compounds represented by the following formula etc. are mentioned, for example, from the point that a CF bond can be introduced into the polymer main chain and the glass transition temperature of the polymer can be increased.

(In the formula, R ⁴¹ represents an alkyl group which may be substituted by one or more fluorine atoms).

（式中，R ⁴²表示可經1個以上之氟原子取代之烷基）。

(In the formula, R ⁴² represents an alkyl group which may be substituted by one or more fluorine atoms).

Examples of the alkyl group of the "alkyl group which may be substituted with one or more fluorine atoms" represented by R ⁴¹ and R ⁴² include methyl group, ethyl group, propyl group, butyl group and the like. Among them, methyl, ethyl, and tert-butyl are preferred, and methyl is more preferred.

Especially preferred is a fluorine-containing acrylic monomer represented by the following formula.

Specific examples of the fluorine-containing acrylic monomer represented by the above formula include methyl 2-fluoroacrylate, ethyl 2-fluoroacrylate, and the like.

As said fluorine-containing acrylic monomer, the monomer represented by the following formula (monomer which has the dicyclopentenyl group represented by said formula (I-1), (I-2)) can also be mentioned. For example, by using these monomers, the dicyclopentenyl group represented by the above-mentioned formulas (I-1) and (I-2) can be introduced into the copolymer.

The fluorine-containing styrene monomer is preferably selected from the group consisting of CF ₂ =CF-C 6 H 5 , CF 2 , and CF 2 : CF-C ₆ H ₅ , CF ₂ At least one of the group consisting of =CF-C ₆ H ₄ -CH ₃ and CF ₂ =CF-C ₆ H ₄ -CF ₃ , among which, the fluorine-containing styrene monomer represented by the following formula is preferred .

As the above-mentioned hydrofluoroolefin, those in which the hydrogen atoms of ethylene are replaced by fluorine atoms are preferred, and examples thereof include vinyl fluoride, trifluoroethylene, and vinylidene fluoride (VDF). Among them, vinyl fluoride is preferred.

The above-mentioned fluorine-containing norbornene only needs to have a polymerizable group, and may have one or a plurality of norbornene skeletons. Fluorine-containing norbornene is produced by the Diels-Alder addition reaction of unsaturated compounds and diene compounds.

Examples of the above-mentioned unsaturated compound include fluorine-containing olefins, fluorine-containing allyl alcohols, fluorine-containing homoallyl alcohols, α-fluoroacrylic acid, α-trifluoromethacrylic acid, fluorine-containing acrylates, and fluorine-containing methacrylates. , 2-(benzoyloxy)pentafluoropropane, 2-(methoxyethoxymethyloxy)pentafluoropropene, 2-(tetrahydropyranyloxy)pentafluoropropene, 2-(benzene formyloxy)trifluoroethylene, 2-(methoxymethyloxy)trifluoroethylene and the like. As said diene compound, cyclopentadiene, cyclohexadiene, etc. are illustrated.

As said fluorine-containing norbornene, the compound represented by the following formula is mentioned, for example.

Among the above-mentioned fluorine-containing monomers, the above-mentioned fluorine-containing monomer preferably contains at least one selected from the group consisting of fluorine-containing ethylene, fluorine-containing propylene, and fluorine-containing vinyl ether, and more preferably contains one selected from the group consisting of fluorine-containing vinylidene At least one selected from the group consisting of fluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, fluoroethylene, hexafluoropropylene, and perfluoro(alkyl vinyl ether).

Moreover, it is preferable that the said fluorine-containing monomer contains at least 1 sort(s) of the compound represented by the following formula, tetrafluoroethylene, and hexafluoropropylene.

Furthermore, it is preferable that the said fluorine-containing monomer contains at least 1 type of compound represented by the following formula.

When the above-mentioned polymer contains the above-mentioned fluorine-containing monomer unit, based on the aspect of excellent low dielectric constant and low dielectric loss tangent, the above-mentioned fluorine-containing monomer unit is relatively small relative to all the polymerized units constituting the above-mentioned copolymer. Preferably at least 1 mol %, more preferably at least 3 mol %, more preferably at least 5 mol %, more preferably at least 80 mol %, more preferably at least 50 mol %, and more preferably at least 50 mol % Below 30 mol%.

The copolymer of the present invention may also contain monomer units other than the above-mentioned aromatic vinyl monomer units, monomer units containing crosslinking groups, monomer units providing a homopolymer with a glass transition temperature of 150°C or higher, and fluorine-containing monomer units "Other monomer units" (polymerized units based on other monomers).

Examples of the above-mentioned other monomers include fluorine-free monomers reactive with the above-mentioned aromatic vinyl monomers, crosslinking group-containing monomers, and monomers that provide homopolymers with a glass transition temperature of 150°C or higher. Monomer (hereinafter also referred to as "fluorine-free monomer"). As said fluorine-free monomer, a hydrocarbon type monomer etc. are mentioned.

Based on the excellent low dielectric constant and low dielectric loss tangent, the above-mentioned other monomer units (polymerized units based on other monomers) are preferably at least 0.1 mol% relative to all the polymerized units constituting the above-mentioned copolymer , more preferably at least 0.5 mol%, more preferably at least 1 mol%, and more preferably at most 50 mol%, more preferably at most 40 mol%, further preferably at most 30 mol%.

Examples of other monomers mentioned above include: Olefins such as ethylene, propylene, butene, isobutene, and 1-decene; Alkyl vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, etc.; Vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl valerate, trimethyl vinyl acetate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl tertiary carbonate Versatic acid vinyl, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl benzoate, p-tert-butyl vinyl benzoate, vinyl cyclohexanecarboxylate Vinyl chloroacetate, Vinyl adipate, Vinyl acrylate, Vinyl methacrylate, Vinyl crotonate, Vinyl sorbate, Vinyl cinnamate, Vinyl undecylenate, Vinyl glycolate , vinyl hydroxypropionate, vinyl hydroxybutyrate, vinyl hydroxyvalerate, vinyl hydroxyisobutyrate, vinyl hydroxycyclohexanecarboxylate and other vinyl esters; Alkyl allyl ethers such as ethyl allyl ether, propyl allyl ether, butyl allyl ether, isobutyl allyl ether, cyclohexyl allyl ether, etc.; Alkyl allyl esters such as ethyl allyl ester, propyl allyl ester, butyl allyl ester, isobutyl allyl ester, cyclohexyl allyl ester, and the like. Among them, olefins and alkyl vinyl ethers are preferred, and 1-decene, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, and cyclohexyl vinyl ether are more preferred. Vinyl ether, 2-ethylhexyl vinyl ether, and more preferably 1-decene, cyclohexyl vinyl ether, and 2-ethylhexyl vinyl ether.

As said other monomer, it is preferable to select the monomer which has an alicyclic structure from the point which can impart solvent solubility to the said copolymer. The monomer having an alicyclic structure is preferably selected from isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentyl acrylate, and dicyclopentyl methacrylate. One or more (meth)acrylates in the group formed.

Regarding the hydrocarbon-based monomer as the above-mentioned other monomer, a functional group-containing hydrocarbon-based monomer can also be used. As the above-mentioned functional group-containing hydrocarbon-based monomer, an OH group-containing monomer and the like may, for example, be mentioned. Examples of the above-mentioned hydrocarbon-based monomers containing functional groups include: hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyisobutyl vinyl ether, hydroxycyclohexyl vinyl ether, and hydroxycyclohexyl vinyl ether. Fluorine-free monomers with OH groups (hydroxyl groups) such as ethers and other hydroxyalkyl vinyl ethers; Itaconic acid, succinic acid, succinic anhydride, fumaric acid, fumaric anhydride, crotonic acid, maleic acid, maleic anhydride, bis(2-ethylhexyl fumarate), etc. body; Glycidyl vinyl ether, glycidyl allyl ether and other fluorine-free monomers with glycidyl groups; Amino alkyl vinyl ether, amino alkyl allyl ether and other fluorine-free monomers with amino groups; Fluorine-free monomers with amide groups such as (meth)acrylamide, hydroxymethylacrylamide, etc.

In terms of excellent low dielectric constant and low dielectric loss tangent, the copolymer of the present invention is preferably a thermosetting resin. For example, a thermosetting resin can be provided by using the above-mentioned aromatic vinyl monomer, crosslinking group-containing monomer, and monomer providing a homopolymer having a glass transition temperature of 150° C. or higher.

The fluorine content of the copolymer of the present invention is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, based on the total mass of the copolymer, and may not contain fluorine. The fluorine content of the above copolymer can be determined by elemental analysis using an automatic sample combustion device.

The number average molecular weight of the copolymer of the present invention is preferably 1,000-50,000. If it exists in such a range, solvent solubility and thermosetting property will improve. The number average molecular weight of the fluorine-containing thermosetting resin is more preferably from 2,000 to 30,000, and still more preferably from 4,000 to 20,000. The number average molecular weight of the above copolymer can be measured by gel permeation chromatography (GPC).

Based on the excellent electrical properties, especially the ability to reduce the dielectric loss tangent, the glass transition temperature of the copolymer of the present invention is preferably 140°C or higher, more preferably 150°C or higher, and more preferably 180°C or higher , and more preferably at least 200°C, especially preferably at least 220°C. The glass transition temperature is preferably higher, but is preferably 300° C. or lower from the viewpoint of workability. The above-mentioned glass transition temperature is a value determined by the mid-point method based on the heat absorption in the second run using a DSC measuring device under the following conditions in accordance with ASTM E1356-98. Measurement conditions Heating rate: 20°C/min Sample size: 10 mg Thermal cycle: -50℃～300℃, heating, cooling, heating

Based on the excellent low dielectric constant and low dielectric loss tangent, the thermosetting temperature of the copolymer of the present invention is preferably below 300°C, more preferably below 270°C, further preferably below 250°C, especially preferably It is below 240°C, most preferably below 230°C. The lower limit is not particularly limited, but it is preferably 80°C or higher, more preferably 100°C or higher. The above-mentioned thermosetting temperature is a value determined by the method described in the following examples.

The copolymer of the present invention preferably has solubility in methyl ethyl ketone (MEK) and toluene. The solubility in MEK was evaluated by the method described in the following examples.

Regarding the copolymer of the present invention, based on the low dielectric constant and low dielectric loss tangent, the dielectric constant (relative dielectric constant) is preferably 2.50 or less, more preferably 2.47 or less, and more preferably 2.30 Below, preferably below 2.25. The lower limit is not particularly limited, and the smaller the value, the more desirable. The above-mentioned permittivity (relative permittivity) is a value determined by the method described in the following examples.

Regarding the copolymer of the present invention, based on the low dielectric constant and excellent low dielectric loss tangent, the dielectric loss tangent is preferably 0.0030 or less, more preferably 0.0028 or less, further preferably 0.0025 or less, especially preferably 0.0025 or less. Below 0.0020. The lower limit is not particularly limited, and the smaller the value, the more desirable. The above-mentioned dielectric loss tangent is a value determined by the method described in the following examples.

The copolymer of the present invention can be produced, for example, by a method for producing a copolymer comprising the steps of appropriately adjusting the composition of the copolymer in the above-mentioned manner, making the above-mentioned aromatic vinyl unit in the presence of a chain transfer agent Polymerize monomers such as monomers, the above-mentioned monomers containing crosslinking groups, and the above-mentioned monomers that provide homopolymers with a glass transition temperature of 150°C or higher.

The copolymer of the present invention can be produced by a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, or a bulk polymerization method during polymerization, and among them, one obtained by a solution polymerization method is preferred.

In the copolymer of the present invention, the above-mentioned aromatic vinyl monomer, the above-mentioned crosslinking group-containing monomer, and the above-mentioned Manufactured by polymerizing monomers such as monomers that provide homopolymers with a glass transition temperature of 150°C or higher. The polymerization temperature is usually 0 to 150°C, preferably 5 to 130°C. The polymerization pressure is usually 0.1 to 10 MPaG (1 to 100 kgf/cm ² G).

烷等環狀醚類；二甲基亞碸等；或該等之混合物等。Examples of the above-mentioned organic solvents include esters such as methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, and tert-butyl acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, Ketones such as cyclohexanone; Aliphatic hydrocarbons such as hexane, cyclohexane, octane, nonane, decane, undecane, dodecane, mineral spirits, etc.; Benzene, toluene, xylene, naphthalene, solvents aromatic hydrocarbons such as solvent naphtha; alcohols such as methanol, ethanol, tertiary butanol, isopropanol, and ethylene glycol monoalkyl ether; tetrahydrofuran, tetrahydropyran,

Cyclic ethers such as alkanes; Dimethylsulfone, etc.; or mixtures thereof, etc.

As the above-mentioned polymerization initiator, for example, persulfates such as ammonium persulfate and potassium persulfate can be used (further, a reducing agent such as sodium bisulfite, sodium metabisulfite, cobalt naphthenate, dimethylaniline, etc. may also be used in combination if necessary) ; redox initiators composed of oxidizing agents (such as ammonium peroxide, potassium peroxide, etc.), reducing agents (such as sodium sulfite, etc.) and transition metal salts (such as ferric sulfate, etc.); acetyl peroxide, benzyl peroxide Acyl, diisobutyryl peroxide, dilauroyl peroxide, didecyl peroxide, dicyclohexyl peroxydicarbonate, bis(4-tertiary butylcyclohexyl) peroxydicarbonate, etc. Acyl peroxides; dialkoxycarbonyl peroxides such as isopropoxycarbonyl peroxide and tertiary butoxycarbonyl peroxide; methyl ethyl ketone peroxide, cyclohexanone peroxide, etc. Ketone peroxide; hydrogen peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide and other hydrogen peroxides; di(tertiary butyl) peroxide, dicumyl peroxide and other two Alkyl peroxides; tert-butyl peroxyacetate, tert-butyl peroxytrimethylacetate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisopropyl monocarbonate Esters, tert-butyl peroxybenzoate, tert-butyl peroxyneodecanoate, tert-butyl peroxylaurate, tert-hexyl peroxytrimethylacetate, peroxy-2-ethylhexanoic acid The third hexyl ester, the third hexyl peroxyisopropyl monocarbonate and other alkyl peroxides; 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-di Methylvaleronitrile), 2,2'-Azobis(2-methylvaleronitrile), 2,2'-Azobis(2-cyclopropylpropionitrile), 2,2'-Azobisiso Azo compounds such as dimethyl butyrate, 2,2'-azobis[2-(hydroxymethyl)propionitrile], 4,4'-azobis(4-cyanopentenoic acid), etc.

As the above-mentioned chain transfer agent, in addition to compounds such as 2,4-diphenyl-4-methylpentene, for example, thiol compounds can be used. As the mercaptan compound, any mercaptan compound known to function as a chain transfer agent will suffice, preferably tertiary (dodecyl) mercaptan, n-dodecyl mercaptan, tertiary octyl mercaptan, n- Octyl mercaptan, trimethylolpropane ginseng-3-mercaptopropionate, neopentylthritol tetra-3-mercaptopropionate, dipenteoerythritol hexa-3-mercaptopropionate and (see-[ (3-mercaptopropionyloxy)ethyl]trimeric isocyanate) and the like. Among them, from the viewpoint of the ease of polymerization control and the toughness of the resulting copolymer, it is particularly preferable to use tertiary (dodecyl) mercaptan, n-dodecyl mercaptan, tertiary octyl mercaptan, n-octyl mercaptan, and n-octyl mercaptan. Monoalkylthiols with 5 to 30 carbon atoms, such as alkylthiols. Also, for example, alcohols may be used, preferably alcohols having 1 to 10 carbon atoms, more preferably monohydric alcohols having 1 to 10 carbon atoms. Specifically, methanol, ethanol, propanol, isopropanol, n-butanol, tert-butanol, 2-methylpropanol, cyclohexanol, methylcyclohexanol, cyclopentanol, methylcyclohexanol, Pentanol, Dimethylcyclopentanol. Among them, methanol, isopropanol, tert-butanol, cyclohexanol, methylcyclohexanol, cyclopentanol, methylcyclopentanol, etc. are preferred, and methanol and isopropanol are particularly preferred.

Among them, 2,4-diphenyl-4-methylpentene is preferred. For example, by combining a diene monomer containing olefins having different reactivity, such as the above-mentioned diene monomer having a dicyclopentenyl group, with 2,4-diphenyl-4-methylpentene, it is possible to prevent the occurrence of polymerization failure. Gelification and introduction of cross-linkable groups in one step.

The copolymer composition (resin composition) of this invention contains the said copolymer, and a solvent. The copolymer composition of the present invention has excellent solvent solubility and thermosetting properties because the copolymer has the above-mentioned constitution. Also, by using it in a resin layer, the resin layer can have a low dielectric constant and a low dielectric loss tangent.

Regarding the copolymer composition of the present invention, the above-mentioned copolymer is the same as the copolymer of the present invention. Therefore, all the preferred aspects of the copolymer described in the copolymer of the present invention can be adopted.

烷等環狀醚類；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等醯胺類；甲苯、二甲苯等芳香族烴類；丙二醇甲基醚等醇類；己烷、庚烷等烴類；該等之混合溶劑等。The copolymer composition of the present invention contains a solvent. The above-mentioned solvent is preferably an organic solvent, and the organic solvent is not particularly limited, and examples thereof include: ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, celloxal acetate, and propylene glycol methyl ether Acetate and other esters; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones; tetrahydrofuran, di

Cyclic ethers such as alkanes; Amides such as N,N-dimethylformamide and N,N-dimethylacetamide; Aromatic hydrocarbons such as toluene and xylene; Alcohols such as propylene glycol methyl ether ; Hydrocarbons such as hexane and heptane; their mixed solvents, etc.

The copolymer composition of the present invention may further include the above-mentioned monomers or other monomer components, for example, may also contain monomer components such as styrene or methyl (meth)acrylate.

-1,4-二基)雙(丙-3,1-二基))雙(1H-吡咯-2,5-二酮)、2,2’-(伸乙二氧基)雙(乙基馬來醯亞胺)、4-(N-馬來醯亞胺甲基)環己烷-1-羧酸羥基琥珀醯亞胺酯、2,2-雙[4-(4-馬來醯亞胺苯氧基)苯基]丙烷等。 本實施方式中使用之聚丁二烯例如可較佳地使用1,2-聚丁二烯。亦可使用市售品，例如可以JSR股份有限公司之製品之形式獲取，此外可自日本曹達股份有限公司獲取製品名為B-1000、2000、3000之液狀聚丁二烯。又，作為可較佳地使用之包含1,2-聚丁二烯結構之共聚物，可例示TOTAL CRAY VALLEY公司之「Ricon100」。本實施方式中使用之馬來醯亞胺類亦可使用市售品，例如可較佳地使用大和化成工業股份有限公司製造之「BMI-2300」、日本化藥股份有限公司製造之「MIR-3000」、K-I Chemical股份有限公司製造之「BMI-70」、K-I Chemical股份有限公司製造之「BMI-80」。 上述共聚物樹脂組成物中之馬來醯亞胺類之含量可根據所期望之特性而適當設定，並無特別限定。於將共聚物組成物中之共聚物固形物成分（樹脂固形物成分）設為100質量份之情形時，馬來醯亞胺化合物之含量較佳為1質量份以上，更佳為5質量份以上。作為上限值，較佳為90質量份以下，更佳為60質量份以下，進而較佳為40質量份以下，亦可為30質量份以下。藉由設為此種範圍，有電氣特性與硬化反應性之平衡良好之傾向。 馬來醯亞胺類可僅使用1種，亦可使用2種以上。於使用2種以上之情形時，較佳為合計量處於上述範圍。 From the viewpoint of improving thermosetting properties, the copolymer composition of the present invention may also contain a crosslinking agent. The crosslinking agent used in this embodiment is not particularly limited as long as it has two or more carbon-carbon unsaturated double bonds in the molecule. That is, as long as the crosslinking agent is capable of reacting with the aromatic vinyl monomer of the present invention, a monomer containing a crosslinking group, and a monomer providing a homopolymer having a glass transition temperature of 150° C. What is necessary is just to form a crosslink and harden it. The crosslinking agent is preferably a compound having two or more carbon-carbon unsaturated double bonds at the end. A crosslinking agent can be used individually or in combination of 2 or more types. Specific examples of crosslinking agents include: triallyl isocyanate (TAIC) and other trienyl isocyanate compounds, the following bismaleimides, or divinylbenzene, (methyl) Dicyclopentenyl acrylate, neopentylthritol tri(meth)acrylate and other monomer components containing multiple vinyl groups, vinyl compounds such as polybutadiene having two or more vinyl groups in the molecule, etc. compounds etc. As the above-mentioned vinyl compound having two or more vinyl groups in the molecule, polymers containing a plurality of vinyl groups such as polybutadiene are preferable. The copolymer composition of the present invention preferably contains the above-mentioned polymer containing a plurality of vinyl groups or the above-mentioned monomer component containing a plurality of vinyl groups. From the viewpoint of improving thermosetting properties, bismaleimides are preferred. As preferred bismaleimides, for example, 1,2-bis(maleimide)ethane, 3-maleimide propionic acid-N-hydroxysuccinimide ester ( N-Succinimidyl 3-maleimidopropionate), 4,4'-diphenylmethane bismaleimide, N,N'-m-phenylene bismaleimide, N,N'-p-phenylene bis Maleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide imide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 1 -maleimide-3-maleimidemethyl-3,5,5-trimethylcyclohexane, 1,1'-(cyclohexane-1,3-diylbis(methylene )) bis(1H-pyrrole-2,5-dione), 1,1'-(4,4'-methylenebis(cyclohexyl-4,1-diyl))bis(1H-pyrrole-2 ,5-diketone), 1,1'-(3,3'-(piper

-1,4-diyl)bis(propane-3,1-diyl))bis(1H-pyrrole-2,5-dione), 2,2'-(ethylenedioxy)bis(ethyl Maleimide), 4-(N-maleimidemethyl)cyclohexane-1-carboxylic acid hydroxysuccinimide ester, 2,2-bis[4-(4-maleimide Aminophenoxy)phenyl]propane, etc. As the polybutadiene used in this embodiment, for example, 1,2-polybutadiene can be preferably used. Commercially available products can also be used. For example, they can be obtained as products of JSR Co., Ltd., and liquid polybutadiene of product names B-1000, 2000, and 3000 can be obtained from Nippon Soda Co., Ltd. Moreover, "Ricon 100" of Total Cray Valley company can be illustrated as the copolymer containing the 1, 2- polybutadiene structure which can be used suitably. The maleimides used in this embodiment can also be commercially available, for example, "BMI-2300" manufactured by Daiwa Chemical Industry Co., Ltd., "MIR-2300" manufactured by Nippon Kayaku Co., Ltd. can be preferably used. 3000", "BMI-70" manufactured by KI Chemical Co., Ltd., and "BMI-80" manufactured by KI Chemical Co., Ltd. The content of maleimides in the above-mentioned copolymer resin composition can be appropriately set according to desired properties, and is not particularly limited. When the copolymer solid content (resin solid content) in the copolymer composition is 100 parts by mass, the content of the maleimide compound is preferably at least 1 part by mass, more preferably 5 parts by mass above. The upper limit is preferably 90 parts by mass or less, more preferably 60 parts by mass or less, further preferably 40 parts by mass or less, and may be 30 parts by mass or less. By setting it as such a range, the balance of electrical characteristics and curing reactivity tends to be favorable. Maleimides may be used alone or in combination of two or more. When using 2 or more types, it is preferable that the total amount exists in the said range.

、2-異丙基-9-氧硫𠮿

、2-氯-9-氧硫𠮿

等9-氧硫𠮿

類；苯乙酮二甲基縮酮、苄基二甲基縮酮等縮酮類；二苯甲酮、4-苯甲醯基-4’-甲基二苯硫醚、4,4’-雙甲基胺基二苯甲酮等二苯甲酮類；2,4,6-三甲基苯甲醯基二苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦等氧化膦類等。 該等可分別單獨使用，亦可併用2種以上。 Furthermore, the above-mentioned polymerization initiator or photopolymerization initiator may also be included. Examples of photopolymerization initiators include: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, and other benzoins; acetophenone, 2,2-diethoxy-2-phenylphenethyl ether Ketone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxy Acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-(N-𠰌linyl)propan-1-one, etc. Ketones; 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone and other anthraquinones; 2,4-diethyl-9-oxosulfur

, 2-isopropyl-9-oxothio𠮿

, 2-Chloro-9-oxosulfur

9-oxosulfur

Ketals; acetophenone dimethyl ketal, benzyl dimethyl ketal and other ketals; benzophenone, 4-benzoyl-4'-methyl diphenyl sulfide, 4,4'- Benzophenones such as dimethylaminobenzophenone; 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl ) phosphine oxides such as phenylphosphine oxide, etc. These may be used individually, respectively, and may use 2 or more types together.

The copolymer composition of the present invention may not contain a crosslinking agent (curing agent), or may not contain a crosslinking agent (curing agent) and a curing accelerator. For example, when the above-mentioned copolymer contains a dicyclopentenyl group, self-crosslinking is possible without using a crosslinking agent or a hardening accelerator. Therefore, electrical characteristics can be improved without adding unnecessary components.

Regarding the copolymer composition of the present invention, the above-mentioned copolymer is preferably at least 10% by mass, more preferably at least 25% by mass, further preferably at least 40% by mass, based on 100% by mass of the solid content, and may be It may be 100 mass % or less, and may be 80 mass % or less.

The copolymer product of the present invention may also contain flame retardants, inorganic fillers, silane coupling agents, release agents, pigments, emulsifiers, and the like.

The copolymer composition of the present invention may also contain various additives according to desired properties. As an additive, a pigment dispersant, an antifoaming agent, a leveling agent, a UV absorber, a light stabilizer, a tackifier, an adhesion improving agent, a matting agent, etc. are mentioned.

The copolymer composition of the present invention preferably has a gel fraction of 30% or more from the viewpoint of thermosetting properties. The above-mentioned gel fraction is more preferably at least 35%, further preferably at least 40%, and especially preferably at least 50%. In addition, the said gel fraction is the value measured by the method described in the following Example.

The preparation method of the copolymer product of the present invention is not particularly limited. For example, the method etc. which mix the solution or dispersion liquid of a copolymer, and other components are mentioned.

The copolymer composition of the present invention can be preferably used as a resin layer of a laminate having a base material and a resin layer provided on the base material, and can be used preferably as a resin layer of a metal-clad laminate. In addition, it can also be used for resins for powder coatings, resins for optical applications, and resist materials. The present invention also relates to a film comprising the above-mentioned copolymer. The present invention also relates to a laminate comprising a substrate and a resin layer provided on the substrate, wherein the resin layer contains the copolymer.

The copolymer composition of the present invention can be preferably used in a metal-clad laminate comprising a metal foil and a resin layer provided on the metal foil, wherein the resin layer is composed of the copolymer of the present invention thing formed. The resin layer can be formed by curing the above-mentioned copolymer composition of the present invention. The present invention also relates to a metal-clad laminate comprising a metal foil and a resin layer provided on the metal foil, wherein the resin layer includes the copolymer.

The above-mentioned metal-clad laminate includes a metal foil and a resin layer. The above-mentioned resin layer has excellent insulating properties and functions as a base material of a metal-clad laminate.

As the metal foil, a metal foil made of copper, aluminum, iron, nickel, chromium, molybdenum, tungsten, zinc, or an alloy thereof can be exemplified, and copper foil is preferable. In addition, in order to improve the adhesion, chemical or mechanical surface treatment can also be performed by siding, nickel plating, copper-zinc alloy plating, or aluminum alcoholate, aluminum chelate, silane coupling agent, etc.

The above-mentioned metal-clad laminate may further include other layers as long as it includes a metal foil and the above-mentioned resin layer, and the metal foil and the above-mentioned resin layer may be one type or two or more types.

The above-mentioned metal-clad laminate may further include a second resin layer provided on the above-mentioned resin layer (hereinafter referred to as "first resin layer"). That is, the metal-clad laminate described above may be one in which a metal foil, a first resin layer, and a second resin layer are laminated in this order. The first resin layer functions as a base material, and also functions as an adhesive layer for bonding the metal foil and the second resin layer. In addition, in the above-mentioned metal-clad laminate, the first resin layer may be provided on a surface of the metal foil that is different from the surface on which the first resin layer is provided (a surface on the opposite side). That is, the metal-clad laminate described above may be one in which the first resin layer, the metal foil, and the first resin layer are sequentially laminated, or the first resin layer, the metal foil, the first resin layer, and the second resin layer are sequentially laminated. Two resin layers.

The above-mentioned second resin layer can use the resin used in conventional printed substrates, and the above-mentioned second resin layer is preferably composed of at least one resin selected from the group consisting of polyethylene terephthalate and polyimide, From the viewpoint of heat resistance, it is more preferably composed of polyimide.

As the first resin layer, a film having a thickness of 1 to 150 μm can be used. When bonding the metal foil and the second resin layer through the first resin layer, the thickness after drying of the first resin layer may be 1 to 100 μm.

As the second resin layer, a resin film having a thickness of 1 to 150 μm can be used.

The above-mentioned metal-clad laminate can be obtained by a production method including the step of adhering a metal foil to a film composed of the above-mentioned copolymer composition to obtain a metal-clad laminate. As the above-mentioned bonding method, a method of heat-compression bonding with a heating press at 50 to 300° C. after overlapping the metal foil and the film containing the above-mentioned copolymer composition is preferred. The above-mentioned production method may further include a step of forming the above-mentioned copolymer composition to obtain a film composed of the above-mentioned copolymer. The molding method may, for example, be a melt extrusion molding method, a solvent casting method, or a spraying method, and is not particularly limited. The above-mentioned copolymer composition may also contain organic solvents, hardeners, etc., and may also contain hardening accelerators, pigment dispersants, defoamers, leveling agents, UV absorbers, light stabilizers, tackifiers, adhesion improvers, Matting agent, etc.

The above-mentioned metal-clad laminate can also be obtained by a production method including the step of coating the above-mentioned copolymer composition on a metal foil to form a first resin layer. The above-mentioned manufacturing method may also include the step of, after the step of forming the above-mentioned first resin layer, further attaching a resin film as the second resin layer on the above-mentioned first resin layer to obtain a metal foil, and a first resin film. And the metal-clad laminate of the second resin layer. The resin film may, for example, be a film made of a resin that can preferably form the second resin layer. As a bonding method of the said resin film, the method of performing thermocompression bonding with a heating press at 50-300 degreeC is preferable. In the above production method, as the method of coating the composition for forming the first resin layer on the metal foil, brush coating, dip coating, spray coating, chipping wheel coating, knife coating, die coating, Die lip coating, roll coater coating, curtain coating and other methods. After coating the composition, it can be cured by drying at 25-200° C. for 1 minute to 1 week using a hot air drying oven or the like.

The above-mentioned metal-clad laminate can also be produced by a production method comprising the steps of: applying the above-mentioned copolymer composition to a resin film as a second resin layer to form a first resin layer; and forming a first resin layer on the first resin layer. A step of adhering the first resin layer of the laminate composed of the second resin layer and the metal foil to obtain a metal-clad laminate having the metal foil and the first and second resin layers. As said resin film, the film which consists of resin which can preferably form a 2nd resin layer is mentioned. As the method of applying the composition for forming the first resin layer on the resin film, brush coating, dip coating, spray coating, chipping wheel coating, knife coating, die coating, lip coating, and roll coating can be mentioned. Machine coating, curtain coating and other methods. After coating the composition, it can be cured by drying at 25-200° C. for 1 minute to 1 week using a hot air drying oven or the like. In the above-mentioned production method, as a method of adhering the metal foil to the first resin layer of the laminate composed of the first resin layer and the second resin layer, it is preferable to make the laminate composed of the first resin layer and the second resin layer A method of thermocompression bonding with a heating press at 50-300°C after overlapping with metal foil so that the first resin layer of the laminate is bonded to the metal foil.

The above-mentioned metal-clad laminate can be used for a printed board having a pattern circuit formed by etching the metal foil of the metal-clad laminate. The present invention also relates to a printed circuit board comprising a pattern circuit formed by etching the metal foil of the metal-clad laminate. The above-mentioned printed substrate can be a flexible substrate or a rigid substrate, preferably a rigid substrate. The printed circuit board may be provided with a coverlay film on the metal-clad laminate, and the coverlay film may be bonded to the metal-clad laminate via the resin layer. The above-mentioned etching method is not limited, and a previously known method can be used. Also, the pattern circuit is not limited, and may be any printed circuit board of the pattern circuit.

The application of the above-mentioned printed substrate is not limited. For example, since the above-mentioned printed circuit board has a resin layer with low dielectric constant and low dielectric loss tangent, it can also be used in applications with high frequency bands such as 4G (37.5 Mbps) and 5G (several G to 20 Gbps). printed substrates. [Example]

Next, the present invention will be described by way of examples, but the present invention is not limited to these examples. Hereinafter, the present invention will be described more specifically by means of examples.

The physical properties described in this specification were measured by the following measurement methods.

(1) NMR analysis Measuring device: NMR measuring device manufactured by VARIAN 1H-NMR measurement conditions: 400 MHz (tetramethylsilane = 0 ppm)

(2) Elemental analysis (determination of fluorine content (mass %)) Measuring device: Automatic sample combustion device (AQF-100 manufactured by Mitsubishi Chemical Co., Ltd.), built-in ion chromatography (ICS-1500 ion chromatography system manufactured by DIONEX Corporation) Sample: 3 mg

(3) Molecular weight Measuring device: Shodex GPC-104 manufactured by Showa Denko Co., Ltd. Determination conditions: THF is used as eluent, and polystyrene with known molecular weight is used as standard sample of molecular weight.

(4) Glass transition temperature According to ASTM E1356-98, using the DSC measuring device manufactured by METLER TOLEDO, according to the heat absorption in the second round, the glass transition temperature and crystal melting point are determined by the midpoint method. Measurement conditions Heating rate: 20°C/min Sample size: 10 mg Thermal cycle: -50℃～300℃, heating, cooling, heating

其中，式中之記號如下所示。 D：空腔共振器直徑（mm） M：空腔共振器單側長度（mm） L：樣品長度（mm） c：光速（m/s） Id：衰減量（dB） F0：共振頻率（Hz） F1：自共振點起之衰減量為3 dB之上側頻率（Hz） F2：自共振點起之衰減量為3 dB之下側頻率（Hz） ε0：真空之介電常數（H/m） εr：樣品之相對介電常數 μ0：真空之磁導率（H/m） Rs：將導體空腔之表面粗糙度亦考慮在內之有效表面電阻（Ω） J0：-0.402759 J1：3.83171 (5) Relative permittivity and dielectric loss tangent A film of the copolymer prepared in the synthesis example was prepared by vacuum hot pressing. The relative permittivity and dielectric loss tangent of the prepared film (sample F) were measured in the following manner. Using a network analyzer, using a cavity resonator, measure the change in the resonant frequency and Q value of the sample F produced above, and calculate the dielectric loss tangent (tanδ) at 12 GHz according to the following formula. The cavity resonator method is based on Professor Kobayashi of Saitama University [Non-destructive measurement of complex dielectric constant of dielectric flat material based on cavity resonator method MW87-53]. tanδ=(1/Qu)×{1+(W2/W1)}－(Pc/ωW1)

However, the symbols in the formula are as follows. D: Diameter of cavity resonator (mm) M: Length of one side of cavity resonator (mm) L: Length of sample (mm) c: Speed of light (m/s) Id: Attenuation (dB) F0: Resonant frequency (Hz ) F1: The frequency at which the attenuation from the resonance point is 3 dB above (Hz) F2: The attenuation from the resonance point is the frequency at the bottom of 3 dB (Hz) ε0: Dielectric constant of vacuum (H/m) εr: relative permittivity of the sample μ0: magnetic permeability of vacuum (H/m) Rs: effective surface resistance taking into account the surface roughness of the conductor cavity (Ω) J0: -0.402759 J1: 3.83171

(6) Evaluation of solvent solubility 20 g of the copolymer prepared in the synthesis example and 30 g of methyl ethyl ketone were weighed into a 100 ml sample bottle, shaken and mixed, and the solubility was checked visually.

(7) Thermosetting evaluation (gel fraction) Take 2 g of the solution prepared in the above solvent solubility evaluation, or the cured composition using a copolymer and a crosslinking agent, into an aluminum cup, heat and dry at each set firing temperature for 1 hour, and obtain a thermosetting product. Take the cured product and wrap it with a pre-weighed 400-mesh wire mesh. Put 25 ml of methyl ethyl ketone and the hardened product wrapped in wire mesh into a 50 ml sample tube, and immerse the hardened product in methyl ethyl ketone for 24 hours. Thereafter, the wire mesh was taken out and dried, the mass after drying was measured, and the mass of the dried hardened product after immersion in methyl ethyl ketone was calculated. The gel fraction was calculated as the mass of the dried cured product after immersion in methyl ethyl ketone/the mass of the cured product before immersion in methyl ethyl ketone×100.

(8) Thermal hardening temperature Regarding the thermosetting temperature, the peak temperature of the exothermic peak observed when measured with a DSC measuring device is used as the thermosetting temperature, or the thermosetting temperature is determined using a differential thermogravimetric measuring device (TG-DTA) (trade name: TG/DTA7200, Hitachi High -Manufactured by Tech Science Co.), 10 mg of the sample is heated from room temperature at a heating rate of 10°C/min, and the peak temperature of the exothermic peak seen in the temperature region where the weight loss does not reach 1% is taken as the heat curing temperature.

(9) Linear expansion rate A film (sample piece) of the copolymer produced in the synthesis example was produced, and the linear expansion rate (linear expansion coefficient) was measured in the following manner. The coefficient of linear expansion of the film was determined by TMA measurement in the following compression mode using TMA-7100 (manufactured by Hitachi High-Tech Science Co., Ltd.). [Tensile mode measurement] As a sample sheet, use an extruded film with a thickness of 760 μm cut to a length of 10 mm and a width of 10 mm, compress it with a load of 49 mN and simultaneously heat it up at a rate of 2°C/min, according to the displacement of the sample at 30 to 200°C to find the linear expansion rate.

＜Synthesis of Copolymer＞ Synthesis Example 1 In a 300 ml four-neck flask, put 100 g of methyl isobutyl ketone, 16 g of styrene, 24 g of dicyclopentenyl vinyl ether, and cyclohexylmaleimide (the glass transition temperature of the homopolymer is 300°C) 24 g, 2,4-diphenyl-4-methyl-1-pentene 0.8 g. The inner temperature was set at 70° C., 2 g of tert-butyl peroxytrimethylacetate was added, and a reaction was performed for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a copolymer. The obtained copolymer was washed with methanol, filtered, and dried to obtain a copolymer. According to NMR analysis, the obtained copolymer had 41 mol% of the structure derived from styrene, 15 mol% of the structure derived from dicyclopentenyl vinyl ether, and 15 mol% of the structure derived from cyclohexylmaleimide. The amine structure is 44 mol% composition. According to the molecular weight analysis, the number average molecular weight (Mn) was 16000, and the weight average molecular weight (Mw) was 41000. The glass transition temperature (Tg) was 180°C. DSC measurement was performed up to 250°C, and as a result, an exothermic peak was confirmed from around 190°C to 250°C.

Synthesis example 2 Into a 300 ml four-neck flask, put 60 g of methyl isobutyl ketone, 11 g of styrene, 14 g of dicyclopentadiene, and 5 g of cyclohexylmaleimide. The inner temperature was set at 90° C., 2 g of tert-butyl peroxy-2-ethylhexanoate was added, and a reaction was performed for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a copolymer. The obtained copolymer was washed with methanol, filtered, and dried to obtain a copolymer. According to elemental analysis and NMR analysis, the obtained copolymer has 60 mol% of the structure derived from styrene, 6 mol% of the structure derived from dicyclopentadiene, and 60 mol% of the structure derived from cyclohexylmaleimide. The amine structure is 34 mol% composition. According to molecular weight analysis, the number average molecular weight (Mn) was 14,000, and the weight average molecular weight (Mw) was 31,000. The glass transition temperature (Tg) was 145°C. (DSC measurement was carried out up to 200°C, and no exothermic peak was confirmed as a result)

Synthesis example 3 In a 300 ml four-neck flask, put 95 g of methyl isobutyl ketone, 12 g of styrene, 15 g of dicyclopentadiene, 20 g of cyclohexylmaleimide, 1,2,2-trifluoroethylene 18 g of phenylbenzene, 4 g of 2,4-diphenyl-4-methyl-1-pentene. The inner temperature was set at 70° C., 2 g of tert-butyl peroxytrimethylacetate was added, and a reaction was performed for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a copolymer. The obtained copolymer was washed with methanol, filtered, and dried to obtain a copolymer. Regarding the obtained copolymer, according to elemental analysis and NMR analysis, the structure derived from 1,2,2-trifluorovinylbenzene (trifluorostyrene) was 6 mol%, and the structure derived from styrene was 59%. Mole %, the structure derived from dicyclopentadiene is 5 mole %, and the structure derived from cyclohexylmaleimide is 30 mole %. According to molecular weight analysis, the number average molecular weight (Mn) was 14,000, and the weight average molecular weight (Mw) was 34,000. The glass transition temperature (Tg) was 161°C. As a result of elemental analysis, the fluorine content was 3.4% by mass. DSC measurement was performed up to 200°C, and as a result, an exothermic peak was confirmed from around 170°C to around 200°C.

Synthesis Example 4 In a 300 ml four-neck flask, put 100 g of methyl isobutyl ketone, 35 g of dicyclopentenyl vinyl ether, 18 g of cyclohexylmaleimide, 2,4-diphenyl-4-methyl Base-1-pentene 2 g. The inner temperature was set at 70° C., 1 g of tert-butyl peroxy-2-ethylhexanoate was added, and the reaction was performed for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a copolymer. The obtained copolymer was washed with methanol, filtered, and dried to obtain a copolymer. According to elemental analysis and NMR analysis, the obtained copolymer has 46 mol% of the structure derived from dicyclopentenyl vinyl ether and 54 mol% of the structure derived from cyclohexylmaleimide. composition. According to molecular weight analysis, the number average molecular weight (Mn) was 4500, and the weight average molecular weight (Mw) was 7800. The glass transition temperature (Tg) was 205°C. DSC measurement was performed similarly, and as a result, an exothermic peak was confirmed around 160°C to 240°C.

Synthesis Example 5 In a 300 ml four-neck flask, put 100 g of methyl isobutyl ketone, 29 g of dicyclopentadiene, 18 g of cyclohexylmaleimide, 2,4-diphenyl-4-methyl-1 - Pentene 2 g. The inner temperature was set to 70° C., 1 g of tert-butyl peroxytrimethylacetate was added, and a reaction was performed for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a copolymer. The obtained copolymer was washed with methanol, filtered, and dried to obtain a copolymer. According to elemental analysis and NMR analysis, the obtained copolymer had a composition of 36 mol% of structures derived from dicyclopentadiene and 64 mol% of structures derived from cyclohexylmaleimide. According to the molecular weight analysis, the number average molecular weight (Mn) was 2000, and the weight average molecular weight (Mw) was 3000. The glass transition temperature (Tg) was 225°C. DSC measurement was performed up to 220°C, and as a result, an exothermic peak was confirmed around 180°C to 220°C.

The polymer composition, physical properties, etc. were measured and evaluated for the polymers produced in Synthesis Examples 1 to 5 and the copolymer films produced using the polymers, and the results are shown in Table 1. Also, the gel fractions of the polymers produced in Synthesis Examples 1 to 5 were measured for cured products produced at the firing temperatures shown in Table 1. The results are described in Table 1.

[Table 1] Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2 Synthesis Example 1 Synthesis example 2 Synthesis example 3 Synthesis Example 4 Synthesis Example 5 polymer composition St/DCPVE/CHMI St/DCPD/CHMI TFS/St/DCPD/CHMI DCPVE/CHMI DCPD/CHMI Fluorine content (mass%) 0 0 3.4 0 0 molecular weight mw 41000 31000 34000 7800 3000 mn 16000 14000 14000 4500 2000 Glass transition temperature (°C) 180 145 161 205 225 Thermal hardening temperature (°C) 210 230 195 200 220 Solvent Solubility Dissolve evenly Dissolve evenly Dissolve evenly Dissolve evenly Dissolve evenly Thermosetting Evaluation Gel Fraction (%) 180°C roasting 2 3 2 10 2 200℃ roasting 3 2 3 33 2 Baking at 220°C 33 2 7 45 8 240℃ roasting 79 40 69 66 12 electrical characteristics Relative permittivity 2.46 2.46 2.21 2.54 2.45 Dielectric loss tangent 0.0028 0.0014 0.00198 0.0044 0.0027 Evaluation of Thermal Properties Linear expansion rate (ppm) - 57 77 - - St: Styrene; DCPVE: Dicyclopentenyl Vinyl Ether; DCPD: Dicyclopentadiene; CHMI: N-Cyclohexylmaleimide; TFS: Trifluorostyrene

＜Production of Copolymer Composition＞ According to the composition in Table 2, a crosslinking agent was blended into the MEK (methyl isobutyl ketone) solution (solid content concentration: 40% by mass (polymer solution)) of the polymer prepared in Synthesis Examples 1 to 3. Solution A (4,4'-diphenylmethanebismaleimide in acetone (concentration 3% by mass)) or cross-linking agent B solution (N,N'-(2,2,4-trimethyl Hexa-1,6-diyl) bismaleimide in methyl ethyl ketone solution (concentration: 10% by mass)) to prepare various hardening compositions. The prepared composition was fired at the firing temperature shown in Table 2 to obtain a cured product, and its gel fraction was measured. The results are described in Table 2.

[Table 2] Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Synthesis Example 1 Synthesis example 2 Synthesis example 3 Synthesis Example 1 Synthesis example 2 Synthesis example 3 Blending amount polymer solution 2 copies 2 copies 2 copies 2 copies 2 copies 2 copies Crosslinker A solution 2.6 servings 2.6 servings 2.6 servings - - - Crosslinker B solution - - - 0.8 parts 0.8 parts 0.8 parts Thermosetting Evaluation Gel Fraction (%) 160°C roasting 2 30 10 1 38 1 180°C roasting 10 68 41 twenty three 75 30 200℃ roasting 60 58 71 40 58 76

From Table 2, it can be confirmed that the addition of the crosslinking agent lowers the curing temperature.

＜Synthesis of Copolymer＞ Synthesis Example 6 In a 300 ml four-neck flask, put 120 parts by mass of methyl isobutyl ketone, 14 parts by mass of styrene, 40 parts by mass of cyclohexylmaleimide, 15 parts by mass of dicyclopentenyl vinyl ether, and Acid bis(2-ethylhexyl) 6 mass parts. The internal temperature was set at 85° C., 0.4 parts by mass of t-butyl peroxy-2-ethylhexanoate was added, and the reaction was performed for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a copolymer. The obtained copolymer was washed with methanol, filtered, and dried to obtain a copolymer. According to NMR analysis, the obtained copolymer had 30 mol% of the structure derived from styrene, 11 mol% of the structure derived from dicyclopentenyl vinyl ether, and 11 mol% of the structure derived from cyclohexylmaleimide. The structure of amine is 56 mol%, and the structure derived from bis(2-ethylhexyl fumarate) is 3 mol%. According to the molecular weight analysis, the number average molecular weight (Mn) is 25728, and the weight average molecular weight (Mw) is 187116. The glass transition temperature (Tg) was 205°C. TG-DTA measurement was carried out up to 600°C, and as a result, a heat generation peak was confirmed from around 190°C to 250°C.

Synthesis Example 7 In a 300 ml four-necked flask, 120 mass parts of methyl isobutyl ketone, 23 mass parts of styrene, 40 mass parts of cyclohexylmaleimide, 13 mass parts of dicyclopentadiene, fumaric acid bis( 2-ethylhexyl ester) 6 parts by mass. The internal temperature was set at 85° C., 0.4 parts by mass of t-butyl peroxy-2-ethylhexanoate was added, and the reaction was performed for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a copolymer. The obtained copolymer was washed with methanol, filtered, and dried to obtain a copolymer. According to NMR analysis, the obtained copolymer has 40 mol% of styrene-derived structure, 5 mol% of dicyclopentadiene-derived structure, and cyclohexylmaleimide-derived structure The composition is 52 mol%, and the structure derived from bis(2-ethylhexyl fumarate) is 3 mol%. According to the molecular weight analysis, the number average molecular weight (Mn) is 29862, and the weight average molecular weight (Mw) is 89407. The glass transition temperature (Tg) was 190°C. TG-DTA measurement was carried out up to 600°C, and as a result, a heat generation peak was confirmed from around 190°C to 250°C.

Synthesis Example 8 In a 300 ml four-necked flask, put 120 parts by mass of methyl isobutyl ketone, 15.6 parts by mass of styrene, 40 parts by mass of cyclohexylmaleimide, 15 parts by mass of dicyclopentenyl vinyl ether, fumarate 6 parts by mass of bis(2-ethylhexyl) and 9 parts by mass of trifluorostyrene. The internal temperature was set at 85° C., 0.2 parts by mass of t-butyl peroxy-2-ethylhexanoate was added, and the reaction was performed for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a copolymer. The obtained copolymer was washed with methanol, filtered, and dried to obtain a copolymer. According to NMR analysis, the obtained copolymer has 3 mol% of trifluorostyrene-derived structure, 33 mol% of styrene-derived structure, and dicyclopentenyl vinyl ether-derived structure The composition is 9 mol%, the structure derived from cyclohexylmaleimide is 52 mol%, and the structure derived from bis(2-ethylhexyl fumarate) is 3 mol%. According to molecular weight analysis, the number average molecular weight (Mn) is 38829, and the weight average molecular weight (Mw) is 249053. The glass transition temperature (Tg) was 195°C. TG-DTA measurement was carried out up to 600°C, and as a result, a heat generation peak was confirmed from around 190°C to 250°C.

Synthesis Example 9 In a 300 ml four-neck flask, put 110 parts by mass of methyl isobutyl ketone, 7.8 parts by mass of styrene, 40 parts by mass of cyclohexylmaleimide, 11.7 parts by mass of dicyclopentadiene, 10 parts by mass of 1-decene parts by mass. The internal temperature was set at 85° C., 0.2 parts by mass of t-butyl peroxy-2-ethylhexanoate was added, and the reaction was performed for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a copolymer. The obtained copolymer was washed with methanol, filtered, and dried to obtain a copolymer. According to NMR analysis, the obtained copolymer has 16 mol% of the structure derived from styrene, 8 mol% of the structure derived from dicyclopentadiene, and the structure derived from cyclohexylmaleimide The composition is 66 mol%, and the structure derived from 1-decene is 10 mol%. According to the molecular weight analysis, the number average molecular weight (Mn) is 26910, and the weight average molecular weight (Mw) is 86654. The glass transition temperature (Tg) was 227°C. TG-DTA measurement was carried out up to 600°C, and as a result, a heat generation peak was confirmed from around 190°C to 250°C.

Synthesis Example 10 120 parts by mass of methyl isobutyl ketone, 18 parts by mass of styrene, 40 parts by mass of cyclohexylmaleimide, 12 parts by mass of dicyclopentadiene, and 6 parts by mass of limonene were put into a 300 ml four-neck flask. The internal temperature was set at 85° C., 0.2 parts by mass of t-butyl peroxy-2-ethylhexanoate was added, and the reaction was performed for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a copolymer. The obtained copolymer was washed with methanol, filtered, and dried to obtain a copolymer. According to NMR analysis, the obtained copolymer has 32 mol% of the structure derived from styrene, 5 mol% of the structure derived from dicyclopentadiene, and the structure derived from cyclohexylmaleimide The composition is 58 mol%, and the structure derived from limonene is 5 mol%. According to molecular weight analysis, the number average molecular weight (Mn) is 22677, and the weight average molecular weight (Mw) is 85014. The glass transition temperature (Tg) was 220°C. TG-DTA measurement was carried out up to 600°C, and as a result, a heat generation peak was confirmed from around 190°C to 250°C.

Synthesis Example 11 In a 300 ml four-neck flask, put 120 parts by mass of methyl isobutyl ketone, 18 parts by mass of styrene, 40 parts by mass of cyclohexylmaleimide, 12 parts by mass of dicyclopentadiene, 2-ethylhexyl 6 parts by mass of vinyl ether. The internal temperature was set at 85° C., 0.2 parts by mass of t-butyl peroxy-2-ethylhexanoate was added, and the reaction was performed for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a copolymer. The obtained copolymer was washed with methanol, filtered, and dried to obtain a copolymer. According to NMR analysis, the obtained copolymer has 34 mol% of the structure derived from styrene, 4 mol% of the structure derived from dicyclopentadiene, and the structure derived from cyclohexylmaleimide The composition is 56 mol%, and the structure derived from 2-ethylhexyl vinyl ether is 6 mol%. According to the molecular weight analysis, the number average molecular weight (Mn) is 5665, and the weight average molecular weight (Mw) is 10242. The glass transition temperature (Tg) was 206°C. TG-DTA measurement was carried out up to 600°C, and as a result, a heat generation peak was confirmed from around 190°C to 250°C.

Synthesis Example 12 In a 300 ml four-neck flask, put 120 parts by mass of methyl isobutyl ketone, 19 parts by mass of styrene, 33 parts by mass of cyclohexylmaleimide, 9 parts by mass of dicyclopentadiene, N-dodecyl 10.3 parts by mass of maleimide. The internal temperature was set at 85° C., 0.2 parts by mass of t-butyl peroxy-2-ethylhexanoate was added, and the reaction was performed for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a copolymer. The obtained copolymer was washed with methanol, filtered, and dried to obtain a copolymer. According to NMR analysis, the obtained copolymer has 43 mol% of the structure derived from styrene, 4 mol% of the structure derived from dicyclopentadiene, and the structure derived from cyclohexylmaleimide The composition is 43 mol%, and the structure derived from N-dodecylmaleimide is 10 mol%. According to the molecular weight analysis, the number average molecular weight (Mn) is 35618, and the weight average molecular weight (Mw) is 124375. The glass transition temperature (Tg) was 162°C. TG-DTA measurement was performed up to 600°C, and as a result, a heat generation peak was confirmed from around 170°C to 250°C.

Synthesis Example 13 In a 300 ml four-neck flask, put 100 parts by mass of methyl isobutyl ketone, 16.2 parts by mass of styrene, 25.3 parts by mass of N-benzylmaleimide, 12 parts by mass of dicyclopentadiene, 1-decane 2.5 parts by mass of alkenes. The internal temperature was set at 85° C., 0.2 parts by mass of t-butyl peroxy-2-ethylhexanoate was added, and the reaction was performed for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a copolymer. The obtained copolymer was washed with methanol, filtered, and dried to obtain a copolymer. According to NMR analysis, the obtained copolymer has 41 mol% of the structure derived from styrene, 3 mol% of the structure derived from dicyclopentadiene, and 3 mol% of the structure derived from N-benzylmaleimide. The composition of the structure is 52 mol%, and the structure derived from 1-decene is 4 mol%. According to the molecular weight analysis, the number average molecular weight (Mn) is 24540, and the weight average molecular weight (Mw) is 98036. The glass transition temperature (Tg) was 162°C. TG-DTA measurement was performed up to 600°C, and as a result, a heat generation peak was confirmed from around 170°C to 250°C.

For the polymers produced in Synthesis Examples 6 to 13 and the films of copolymers produced using the polymers, polymer compositions, physical properties, etc. were measured and evaluated, and the results are shown in Table 3. Also, the gel fractions of the polymers produced in Synthesis Examples 6 to 13 were measured for cured products produced at the firing temperatures shown in Table 3. The results are described in Table 3.

[table 3] Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 Synthesis Example 9 Synthesis Example 10 Synthesis Example 11 Synthesis Example 12 Synthesis Example 13 polymer composition St/DCPVE/CHMI/2EHFM St/DCPD/CHMI/2EHFM TFS/St/DCPVE/CHMI/2EHFM St/DCPD/CHMI/1DE St/DCPD/CHMI/LM St/DCPD/CHMI/2EHVE St/DCPD/CHMI/DMI St/DCPD/BzMI/1DE Fluorine content (mass%) 0 0 0.8 0 0 0 0 0 molecular weight mw 187116 89407 249053 86654 85014 10242 124375 98036 mn 25728 29862 38829 26910 22677 5665 35618 24540 Glass transition temperature (°C) 205 190 195 227 220 206 162 162 Thermal hardening temperature (°C) 215 210 228 220 220 220 210 210 Solvent Solubility Dissolve evenly Dissolve evenly Dissolve evenly Dissolve evenly Dissolve evenly Dissolve evenly Dissolve evenly Dissolve evenly Thermosetting Evaluation Gel Fraction (%) 180°C roasting 94 2 92 77 2 3 16 84 200℃ roasting 93 75 96 81 56 87 90 90 240℃ roasting 95 90 99 94 88 90 86 87 electrical characteristics Relative permittivity 2.32 2.43 2.46 2.47 2.45 2.53 2.51 2.53 Dielectric loss tangent 0.0019 0.0019 0.0020 0.0010 0.0012 0.0016 0.0013 0.0013 St: Styrene; DCPVE: Dicyclopentenyl Vinyl Ether; DCPD: Dicyclopentadiene; CHMI: N-Cyclohexylmaleimide; TFS: Trifluorostyrene 2EHFM: bis(2-ethylhexyl fumarate); 1DE: 1-decene; LM: limonene; 2EHVE: 2-ethylhexyl vinyl ether; DNI: N-dodecylmaleimide; BzMI: N-Benzylmaleimide

Example 18 10 parts by mass of the polymer obtained in Synthesis Example 9, 2 parts by mass of polybutadiene (B-2000 manufactured by Nippon Soda Co., Ltd.), and 0.1 parts by mass of an initiator (PERCUMYL D-40 manufactured by NOF Corporation) Parts by mass were dissolved in 48 parts by mass of methyl isobutyl ketone to prepare a copolymer composition. A prepreg was produced by impregnating the obtained copolymer composition into glass cloth, and then heating and drying at 100° C. for about 3 minutes. The above-mentioned glass cloth is specifically ♯1035 type E glass manufactured by Asahi Kasei Co., Ltd. (density: 2.6 g/cm ³ ; weight per 1 m ² : 29.1 g; measured value of glass cloth thickness: 29 μm; relative dielectric Constant measured value: 2.66; dielectric loss tangent measured value: 0.0048). At this time, it adjusted so that content (resin content rate) of the copolymer composition might become about 40 mass %. Next, four prepregs were stacked, and heated and pressurized for 120 minutes at a temperature of 250°C and a pressure of 2.44 MPa (megapascals), to produce a test body. The thickness of this test body was 132.2 μm. The relative permittivity and dielectric loss tangent of the test body were measured. As a result, the relative permittivity was 3.37, the dielectric loss tangent was 0.00522, and the gel fraction was 67%. According to the measured values of the relative permittivity and dielectric loss tangent of the test body, the relative permittivity and dielectric loss tangent of the hardened polymer were calculated using the following formula. As a result, the relative permittivity was 2.55 and the dielectric loss tangent was 0.00145 . Dielectric loss tangent of test body = dielectric loss tangent of glass wiring × glass cloth vol%/100 + hardened polymer dielectric loss tangent × hardened polymer vol%/100 Glass cloth dielectric loss tangent = glass wiring dielectric loss tangent ×Glass wiring vol%/100+Air dielectric loss tangent×Air vol%/100 Glass cloth vol%=Glass cloth weight per 1 ^m2 /Glass cloth density/Prepreg in impregnated test body per 1 piece The thickness of hardened polymer vol% = 1 - glass cloth vol%

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Claims (23)

A copolymer comprising an aromatic vinyl monomer unit, a monomer unit containing a crosslinking group, and a monomer unit providing a homopolymer with a glass transition temperature above 150°C. The copolymer of claim 1, which is a thermosetting resin. The copolymer according to claim 1 or 2, wherein the above-mentioned aromatic vinyl monomer units are styrene units. The copolymer according to any one of claims 1 to 3, wherein the above-mentioned monomer unit containing a crosslinking group comprises a diene monomer unit having an alicyclic structure. The copolymer according to any one of claims 1 to 3, wherein the monomer unit containing a crosslinking group includes a monomer unit having a dicyclopentenyl structure. The copolymer according to any one of claims 1 to 3, wherein the above-mentioned monomer unit containing a crosslinking group comprises a group selected from dicyclopentadiene units and dicyclopentenyl vinyl ether units. at least one. The copolymer according to any one of claims 1 to 6, wherein the above-mentioned monomer units providing a homopolymer having a glass transition temperature of 150° C. or higher include maleimide units. The copolymer of claim 7, wherein the above-mentioned maleimide units include at least one selected from the group consisting of N-cyclohexylmaleimide units and N-phenylmaleimide units . The copolymer according to any one of claims 1 to 8, further comprising a fluorine-containing monomer unit providing a C-F bond to the main chain. The copolymer according to any one of claims 1 to 9, which has a glass transition temperature of 140°C or higher. The copolymer according to any one of Claims 2 to 10, which has a thermosetting temperature of 240°C or lower. The copolymer according to any one of claims 1 to 11, which has solubility in methyl ethyl ketone or toluene. The copolymer according to any one of claims 1 to 12, wherein the monomer unit containing a crosslinking group is 1 mol% or more relative to all polymerized units constituting the copolymer. The copolymer according to any one of claims 1 to 13, wherein, relative to all the polymerized units constituting the above-mentioned copolymer, the above-mentioned monomer units providing a homopolymer having a glass transition temperature of 150° C. or higher is 5 mol% or more . The copolymer according to any one of claims 1 to 14, which has a dielectric loss tangent of 0.0030 or less. A copolymer composition comprising the copolymer according to any one of claims 1 to 15, and a solvent. The copolymer composition according to claim 16, which contains a polymer containing multiple vinyl groups or a monomer component containing multiple vinyl groups. The copolymer composition according to claim 16 or 17, which contains a photopolymerization initiator. As the copolymer composition according to any one of claims 16 to 18, its gel fraction is more than 30%. A film comprising the copolymer according to any one of claims 1 to 15. A laminate comprising a substrate and a resin layer provided on the substrate, wherein the resin layer includes the copolymer according to any one of claims 1 to 15. A metal-clad laminate comprising a metal foil and a resin layer provided on the metal foil, and the resin layer includes the copolymer according to any one of claims 1 to 15. A printed circuit board characterized by comprising a pattern circuit formed by etching the metal foil of the metal-clad laminate of claim 22.