CN117897416A - Copolymer and resin composition - Google Patents

Copolymer and resin composition Download PDF

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Publication number
CN117897416A
CN117897416A CN202280054502.5A CN202280054502A CN117897416A CN 117897416 A CN117897416 A CN 117897416A CN 202280054502 A CN202280054502 A CN 202280054502A CN 117897416 A CN117897416 A CN 117897416A
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Prior art keywords
copolymer
monomer
mol
monomer unit
group
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Inventor
石川卓司
福原良成
穗垣良弥
川部琢磨
井本克彦
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Daikin Industries Ltd
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Daikin Industries Ltd
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Priority claimed from JP2022108931A external-priority patent/JP7339576B2/en
Application filed by Daikin Industries Ltd filed Critical Daikin Industries Ltd
Priority claimed from PCT/JP2022/029967 external-priority patent/WO2023022010A1/en
Publication of CN117897416A publication Critical patent/CN117897416A/en
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Abstract

The purpose of the present invention is to provide a copolymer having excellent solvent solubility and low dielectric loss tangent. A copolymer comprising an aromatic vinyl monomer unit, a monomer unit containing a crosslinking group, and a monomer unit providing a homopolymer having a glass transition temperature of 150 ℃ or higher.

Description

Copolymer and resin composition
Technical Field
The present invention relates to a copolymer and a resin composition.
Background
In recent years, electric devices, electronic devices, and communication devices have been developed significantly. Currently, in these devices, frequencies of higher frequency bands tend to be used. In general, various printed substrates are used in these devices. Therefore, a printed board is also required to have excellent electrical characteristics corresponding to frequencies in a high frequency band, excellent heat resistance capable of withstanding soldering operations, and the like.
For example, patent document 1 discloses an invention related to a composition containing a predetermined fluorine-containing thermosetting resin, a siloxane compound, and a catalyst for hydrosilylation reaction. However, specifically disclosed as the fluorine-containing thermosetting resin are resins in which a crosslinking group is introduced into an OH group-containing fluororesin by a polymer reaction.
Patent document 2 discloses an invention relating to a predetermined laminate, and describes the use of a fluorine-containing thermosetting resin to introduce a crosslinking group. However, only introduction of a crosslinking group or the like into an OH group-containing fluororesin by a polymer reaction has been described.
Patent document 3 discloses an invention related to a predetermined curable resin composition comprising a fluoropolymer and a hydrosilylated crosslinking agent, and describes an example of dicyclopentadiene and fluoroolefin. However, the polymerization efficiency cannot be said to be good. In addition, a curing system using a crosslinking agent in combination is disclosed, but a curing reaction using only heat is not disclosed.
Prior art literature
Patent literature
Patent document 1: international publication No. 2008/044765
Patent document 2: japanese patent laid-open publication No. 2014-26619
Patent document 3: international publication No. 2011/115042
Disclosure of Invention
Problems to be solved by the invention
The present invention provides a copolymer having excellent solvent solubility and low dielectric loss tangent.
Means for solving the problems
The present invention (1) relates to a copolymer comprising: an aromatic vinyl monomer unit, a monomer unit containing a crosslinking group, and a monomer unit providing a homopolymer having a glass transition temperature of 150 ℃ 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 of the present invention (1) or (2), wherein the aromatic vinyl monomer unit is a styrene unit.
The present invention (4) is a copolymer in any combination with any one of the present inventions (1) to (3), wherein the monomer unit containing a crosslinking group contains a diene monomer unit having an alicyclic structure.
The present invention (5) is a copolymer in any combination with any one of the present invention (1) to (3), wherein the monomer unit containing a crosslinking group contains a monomer unit having a dicyclopentenyl structure.
The present invention (6) is a copolymer in any combination with any of the present inventions (1) to (3), wherein the monomer unit containing a crosslinking group contains at least 1 selected from the group consisting of dicyclopentadiene units and dicyclopentenyl 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 monomer unit providing a homopolymer having a glass transition temperature of 150 ℃ or higher contains a maleimide-based unit.
The present invention (8) is the copolymer of the present invention (7), wherein the maleimide-based unit comprises at least 1 selected from the group consisting of an N-cyclohexylmaleimide unit and an N-phenylmaleimide unit.
The present invention (9) is a copolymer in any combination with any of the present invention (1) to (8), further comprising a fluorine-containing monomer unit providing a C-F bond to the main chain.
The present invention (10) is a copolymer having a glass transition temperature of 140℃or higher, in any combination with any of the present invention (1) to (9).
The copolymer of the present invention (11) in any combination with any one of the present invention (2) to (10) has a heat curing temperature of 240℃or lower.
The present invention (12) is a copolymer in any combination with any one of the present invention (1) to (11), which has solubility in methyl ethyl ketone or toluene.
The present invention (13) is a copolymer in any combination with any one of the present inventions (1) to (12), wherein the monomer unit containing a crosslinking group is 1 mol% or more with respect to all the polymerization units constituting the copolymer.
The present invention (14) is a copolymer in any combination with any one of the present inventions (1) to (13), wherein the monomer unit providing a homopolymer having a glass transition temperature of 150 ℃ or higher is 5 mol% or more with respect to all the polymerized units constituting the copolymer.
The copolymer of the present invention (15) in any combination with any one of the present invention (1) to (14) has a dielectric loss tangent of 0.0030 or less.
The present invention (16) relates to a copolymer composition comprising a copolymer and a solvent in any combination with any of the present invention (1) to (15).
The present invention (17) is a copolymer composition of the present invention (16), comprising: a polymer containing 2 or more vinyl groups or a monomer component containing 2 or more vinyl groups.
The present invention (18) is the copolymer composition of the present invention (16) or (17), which contains a photopolymerization initiator.
The copolymer composition of the present invention (19) is a copolymer composition in any combination with any of the above (16) to (18), and has a gel fraction of 30% or more.
The present invention (20) relates to a film comprising a copolymer in any combination with any of the present invention (1) to (15).
The present invention (21) relates to a laminate comprising a base material and a resin layer provided on the base material, wherein the resin layer contains a copolymer in any combination with any one of the present inventions (1) to (15).
The present invention (22) relates to a metal-clad laminate comprising a metal foil and a resin layer provided on the metal foil, wherein the resin layer comprises a copolymer in any combination with any one of the present inventions (1) to (15).
The present invention (23) relates to a printed circuit board comprising a pattern circuit formed by etching a metal foil of the metal-clad laminate of the present invention (22).
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a copolymer excellent in solvent solubility and low dielectric loss tangent can be provided.
Detailed Description
As described in patent documents 1 and 2, it is generally necessary to introduce a crosslinking group in order to prepare a thermosetting resin from a resin (polymer). In addition, conventionally, the introduction of a crosslinking group has been generally a method of synthesizing a polymer containing an OH group and introducing an acryl group by a polymer reaction, and particularly a method of introducing an acrylic monomer having an isocyanate by reacting with an OH group has been simple and widely used. However, the electric characteristics of the resin having an acryl group as a crosslinking group are not good. As another method, there is a method of copolymerizing diene monomers at the time of polymerization simply, but there is a problem that gelation occurs during polymerization or the amount of introduced crosslinking groups is limited.
The inventors have found through intensive studies that a copolymer (resin) using the aromatic vinyl monomer of the present invention, a monomer having a crosslinking group, and a monomer providing a homopolymer having a glass transition temperature of 150℃or higher can provide a copolymer excellent in solvent solubility and low dielectric loss tangent, and have completed 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 having a glass transition temperature of 150 ℃ or higher. The copolymer has these 3 units, and thus is endowed with very low dielectric loss tangent and excellent solvent solubility. In addition, the dielectric constant and the linear expansion coefficient are also low. Furthermore, since a monomer unit containing a crosslinking group is introduced, self-crosslinking (thermal crosslinking or the like) can be performed even without using a crosslinking agent in particular, and excellent thermosetting properties can be imparted.
The copolymers of the present invention have aromatic vinyl monomer units.
An "aromatic vinyl monomer unit" is a polymerized unit based on an aromatic vinyl monomer. The copolymer may contain 1 kind of aromatic vinyl monomer unit or 2 or more kinds of aromatic vinyl monomer units. The aromatic vinyl monomer unit may be any of a fluorine-containing monomer unit (a polymerized unit based on a fluorine-containing monomer) and a non-fluorine-containing monomer unit (a polymerized unit based on a non-fluorine-containing monomer).
The aromatic vinyl monomer is a monomer having an aromatic ring and a vinyl group in the molecule, and examples thereof include styrene, α -methylstyrene, p-methylstyrene, o-methylstyrene, and t-butylstyrene. Among the above aromatic vinyl monomer units, styrene units are preferred in terms of low dielectric constant and low dielectric loss tangent.
The aromatic vinyl monomer unit is preferably 5 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, and further preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less, based on the total polymerized units constituting the copolymer, because of excellent low dielectric constant and low dielectric loss tangent.
The copolymers of the invention have monomer units containing crosslinking groups.
The "crosslinking group-containing monomer unit" is a polymerized unit based on a crosslinking group-containing monomer (crosslinking group-containing monomer). The copolymer may contain 1 kind of monomer unit containing a crosslinking group, or may contain 2 or more kinds. The monomer unit containing a crosslinking group may be any of a fluorine-containing monomer unit and a non-fluorine-containing monomer unit.
The crosslinking group-containing monomer is a crosslinking group (a group having crosslinkability) in the molecule. Examples of the crosslinking group include a group containing a carbon-carbon double bond, a halogen atom, an acid anhydride group, a carboxyl group, an amino group, a cyano group, a hydroxyl group, and the like.
The monomer unit containing a crosslinking group is preferably 1 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, and further preferably 50 mol% or less, more preferably 30 mol% or less, still more preferably 20 mol% or less, based on the total of the polymerized units constituting the copolymer, because of excellent low dielectric constant and low dielectric loss tangent.
The monomer unit containing a crosslinking group is not particularly limited as long as it is a monomer unit having a crosslinking group, and a diene monomer unit having an alicyclic structure (a polymerized unit based on a diene monomer having an alicyclic structure) is preferable in terms of a low dielectric constant and a low dielectric loss tangent.
Examples of the diene monomer having an alicyclic structure include monocyclic alicyclic dienes, polycyclic alicyclic condensed dienes, and crosslinked cyclic dienes. Examples of the monocyclic alicyclic diene include 1, 4-cyclohexadiene, 1, 5-cyclooctadiene, 1, 5-cyclododecadiene, 4-vinylcyclohexene, 1-allyl-4-isopropenylcyclohexane, 3-allylcyclopentene, 1-isopropenyl-4- (4-butenyl) cyclohexane, and limonene. Examples of the polycyclic alicyclic condensed dienes and crosslinked cyclic dienes include tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, bicyclo (2, 1) hept-2, 5-diene, 2-methylbicycloheptadiene, alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornene (5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropylidene norbornene, 5- (4-cyclopentenyl) -2-norbornene, 5-cyclohexylidene-2-norbornene, and the like). Among them, limonene, dicyclopentadiene, 5-ethylidene-2-norbornene are preferable.
As the monomer unit containing a crosslinking group, at least 1 selected from the group consisting of dicyclopentadiene units (polymerized units based on dicyclopentadiene) and monomer units having a dicyclopentenyl structure (polymerized units based on a monomer having a dicyclopentenyl structure) is also preferable from the viewpoints of low dielectric constant and low dielectric loss tangent. 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 hetero atom.
Among the above-mentioned monomer units having a crosslinking group, at least 1 selected from the group consisting of dicyclopentadiene units and dicyclopentenyl vinyl ether units is preferable.
The dicyclopentadiene (DCPD) is a monomer represented by the following formula.
[ chemical 1]
The dicyclopentadiene unit is preferably 1 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, and further preferably 50 mol% or less, more preferably 30 mol% or less, still more preferably 20 mol% or less, based on the total polymerized units constituting the copolymer, because of excellent low dielectric constant and low dielectric loss tangent.
Examples of the monomer having the above-mentioned dicyclopentenyl structure include monomers having dicyclopentenyl groups represented by the following formulas (I-1) and (I-2).
[ chemical 2]
Examples of the monomer having a dicyclopentadienyl group represented by the above-mentioned formulas (I-1) and (I-2) include the following compounds.
[ chemical 3]
(wherein R is 51 Is a hydrogen atom or a methyl group. )
Among them, preferred are compounds represented by the following formula.
[ chemical 4]
As specific examples of the monomer having a dicyclopentenyl group represented by the above-mentioned formulas (I-1) and (I-2), dicyclopentenyl acrylate, dicyclopentenyl methacrylate and the like can be given.
The monomer having the dicyclopentadienyl group represented by the above-mentioned formulas (I-1) and (I-2) may be exemplified by the following compounds.
[ chemical 5]
(wherein R is 61 Is a hydrogen atom or a methyl group. )
Among them, preferred are compounds represented by the following formula.
[ chemical 6]
As specific examples of the monomer having a dicyclopentenyl group represented by the above-mentioned formulas (I-1) and (I-2), dicyclopentenyl vinyl ether and the like can be exemplified.
The monomer unit containing the dicyclopentenyl structure is preferably 1 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, and further preferably 50 mol% or less, more preferably 30 mol% or less, still more preferably 20 mol% or less, with respect to the total of the polymerized units constituting the copolymer, because of excellent low dielectric constant and low dielectric loss tangent.
The copolymer of the present invention has the above-mentioned monomer unit providing a homopolymer having a glass transition temperature (Tg) of 150 ℃ or higher (a polymerized unit based on a monomer providing a homopolymer having a Tg of 150 ℃ or higher). The "monomer unit providing a homopolymer having a glass transition temperature of 150 ℃ or higher" is a polymerized unit based on a monomer having a glass transition temperature of 150 ℃ or higher when a homopolymer obtained by polymerizing only the same kind of monomer is produced. The copolymer may contain 1 kind of such monomer unit or 2 or more kinds. The monomer unit may be any of a fluorine-containing monomer unit and a non-fluorine-containing monomer unit.
Among the above monomer units which provide a homopolymer having a glass transition temperature (Tg) of 150 ℃ or higher, the Tg is preferably 170 ℃ or higher, more preferably 200 ℃ or higher, still more preferably 250 ℃ or higher, and further preferably 400 ℃ or lower, more preferably 350 ℃ or lower, still more preferably 320 ℃ or lower.
The Tg is a value measured by a Differential Scanning Calorimeter (DSC).
The monomer unit providing a homopolymer having a glass transition temperature of 150 ℃ or higher is preferably 5 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, and further preferably 80 mol% or less, still more preferably 70 mol% or less, still more preferably 60 mol% or less, with respect to all the polymerized units constituting the copolymer, because of excellent low dielectric constant and low dielectric loss tangent.
The monomer unit providing a homopolymer having a glass transition temperature of 150℃or higher preferably contains a maleimide unit (maleimide-based monomer unit), more preferably contains an N-substituted maleimide unit (N-substituted maleimide-based monomer unit), because of its excellent low dielectric constant and low dielectric loss tangent. Among them, the monomer unit represented by the following formulas (II-1) and (II-2) is preferably contained.
[ chemical 7]
(wherein R is 11 Is an arylalkyl group having 7 to 14 carbon atoms or an aryl group having 6 to 14 carbon atoms. R is R 12 And R is 13 Each independently represents a hydrogen atom, an oxygen atom, a sulfur atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 14 carbon atoms. R is as follows 11 、R 12 、R 13 With or without substituents. )
[ chemical 8]
(wherein R is 14 Is a hydrogen atom, a cycloalkyl group having 3 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms. R is R 15 And R is 16 Each independently represents a hydrogen atom, an oxygen atom, a sulfur atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 14 carbon atoms. R is as follows 14 、R 15 、R 16 With or without substituents. )
R as the above formula (II-1), (II-2) 11 ～R 16 Examples of the substituent(s) include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, and a benzyl group.
Examples of the monomer forming the monomer unit represented by the above formula (II-1) include N-arylmaleimides and N-aromatic substituted maleimides. Specifically, N-phenylmaleimide, N-benzylmaleimide, N- (2-chlorophenyl) maleimide, N- (4-bromophenyl) maleimide, N- (2-methylphenyl) maleimide, N- (2, 6-dimethylphenyl) 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-anthrylmaleimide, 3-methyl-1-phenyl-1H-pyrrole-2, 5-dione, 3, 4-dimethyl-1-phenyl-1H-pyrrole-2, 5-dione, 1, 3-diphenyl-1H-pyrrole-2, 5-dione, 3, 4-triphenyl-1, 5-dione and the like can be mentioned. Among them, N-phenylmaleimide and N-benzylmaleimide are preferable, and N-phenylmaleimide is more preferable, from the viewpoints of low dielectric constant and low dielectric loss tangent.
The monomer unit represented by the formula (II-1) is preferably 5 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, and further preferably 80 mol% or less, more preferably 70 mol% or less, still more preferably 60 mol% or less, based on the total of the polymerized units constituting the copolymer, because of excellent low dielectric constant and low dielectric loss tangent.
Examples of the monomer forming the monomer unit represented by the above formula (II-2) include N-methylmaleimide, N-ethylmaleimide, N-N-propylmaleimide, N-isopropylmaleimide, N-N-butylmaleimide, N-isobutylmaleimide, N-sec-butylmaleimide, N-tert-butylmaleimide, N-N-pentylmaleimide, N-N-hexylmaleimide, N-N-heptylmaleimide, N-N-octylmaleimide, N-laurylmaleimide, N-2-ethylhexyl maleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cyclohexylmethylmaleimide, 1-cyclohexyl-3-methyl-1H-pyrrole-2, 5-dione, 1-cyclohexyl-3, 4-dimethyl-1H-pyrrole-2, 5-dione, 1-cyclohexyl-3-phenyl-1H-pyrrole-2, 5-dione, 1-cyclohexyl-3, 4-diphenyl-2, 5-dione and the like. Among them, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide and N-cyclohexylmaleimide are preferred from the viewpoint of low dielectric constant and low dielectric loss tangent, and N-cyclohexylmaleimide is more preferred.
The monomer unit represented by the formula (II-2) is preferably 5 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, and further preferably 80 mol% or less, more preferably 70 mol% or less, still more preferably 60 mol% or less, based on the total of the polymerized units constituting the copolymer, because of excellent low dielectric constant and low dielectric loss tangent.
The total unit amount of the monomer units represented by the formulae (II-1) and (II-2) is preferably 5 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, and further preferably 80 mol% or less, still more preferably 70 mol% or less, still more preferably 60 mol% or less, based on the total of all the polymerization units constituting the copolymer, because of excellent low dielectric constant and low dielectric loss tangent.
The maleimide-based unit preferably contains at least 1 selected from the group consisting of an N-cyclohexylmaleimide unit and an N-phenylmaleimide unit.
The molar ratio of the aromatic vinyl monomer unit/the monomer unit containing a crosslinking group of the copolymer of the present invention is preferably (50 to 95)/(5 to 50), more preferably (55 to 95)/(5 to 45), and still more preferably (60 to 95)/(5 to 40) from the viewpoints of low dielectric constant and low dielectric loss tangent.
In the copolymer of the present invention, the molar ratio of the monomer units to the monomer units containing a crosslinking group, which provides a homopolymer having a glass transition temperature of 150℃or higher, is preferably (50 to 95)/(5 to 50), more preferably (60 to 90)/(10 to 40), and still more preferably (65 to 90)/(10 to 35), from the viewpoints of low dielectric constant and low dielectric loss tangent.
In the copolymer, the total content of the aromatic vinyl monomer unit, the monomer unit containing a crosslinking group, and the monomer unit providing a homopolymer having a glass transition temperature of 150 ℃ or higher is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and particularly preferably 97 mol% or more, with respect to all the polymerized units. It may be 100 mol% with respect to the total polymerized units.
From the viewpoints of low dielectric constant and low dielectric loss tangent, the copolymer of the present invention preferably further has a fluorine-containing monomer unit (hereinafter also simply referred to as "fluorine-containing monomer unit") that provides a C-F bond to the main chain. In this case, the copolymer contains a fluorine atom, and has a C-F bond between a carbon atom forming the main chain and the fluorine atom.
The above-mentioned fluoromonomer unit (polymerized unit based on fluoromonomer) can be introduced into the copolymer by using fluoromonomer. The fluorine-containing monomer may be any of a cyclic monomer and an acyclic monomer. The cyclic monomer and the acyclic monomer preferably have a C-F bond between a carbon atom and a fluorine atom forming the main chain of the copolymer.
Examples of the fluorine-containing monomer include a fluorine-containing vinyl monomer, a fluorine-containing acrylic monomer, a fluorine-containing styrene monomer, a hydrogen-containing fluoroolefin, and a fluorine-containing norbornene. Among them, a fluorine-containing vinyl monomer and a fluorine-containing acrylic monomer are preferable.
The fluorine-containing vinyl monomer is preferably at least 1 selected from the group consisting of tetrafluoroethylene [ TFE ], chlorotrifluoroethylene [ CTFE ], hexafluoropropylene [ HFP ] and perfluoro (alkyl vinyl ether), more preferably at least 1 selected from the group consisting of TFE, CTFE, HFP and perfluoro (alkyl vinyl ether). From the viewpoint of being excellent in low dielectric constant and low dielectric loss tangent, dispersibility, moisture resistance, heat resistance, flame retardancy, adhesion, chemical resistance, and the like, and also from the viewpoint of being excellent in low dielectric constant and low dielectric loss tangent, weather resistance, and moisture resistance, at least 1 selected from the group consisting of TFE, CTFE, and HFP is more preferable, at least 1 selected from the group consisting of TFE and HFP is further preferable from the viewpoint of not containing chlorine, and TFE is particularly preferable from the viewpoint of being excellent in copolymerization.
Examples of the perfluoro (alkyl vinyl ether) include perfluoro (methyl vinyl ether) [ PMVE ], perfluoro (ethyl vinyl ether) [ PEVE ], perfluoro (propyl vinyl ether) [ PPVE ], perfluoro (butyl vinyl ether) and the like, but are not limited thereto.
Among the above-mentioned fluorine-containing vinyl monomers, preferred are fluorine-containing vinyl, fluorine-containing propylene, fluorine-containing vinyl ether and the like, and more preferred are tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene and perfluoro (alkyl vinyl ether).
Particularly preferred are fluorovinyl monomers represented by the following formula.
[ chemical 9]
(wherein R is 71 ～R 74 Independently of one another, are 1-valent radicals, R 71 ～R 73 At least 1 of them is a fluorine atom or CF 3 A base. )
As R 71 ～R 74 Examples of the 1-valent group of (a) include a hydrogen atom, a halogen atom (e.g., a fluorine atom and a chlorine atom), and a 1-valent hydrocarbon group.
The 1-valent hydrocarbon group may have a hetero atom such as a nitrogen atom and an oxygen atom. The 1-valent hydrocarbon group may be any of a linear, branched, and cyclic hydrocarbon group. The number of carbon atoms of the 1-valent hydrocarbon group is preferably 1 to 8, more preferably 1 to 5, and still more preferably 1 to 3. Examples of the 1-valent hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, and the like having the above carbon number.
The 1-valent group is preferably a hydrogen atom, a fluorine atom, a chlorine atom, a fluoroalkyl group having the above carbon number, or a fluoroalkoxy group having the above carbon number.
The fluorine-containing acrylic monomer may be a compound represented by the following formula, for example, in order to introduce a c—f bond into the polymer main chain and to raise the glass transition temperature of the polymer.
[ chemical 10]
(wherein R is 41 Represents an alkyl group which may be substituted with 1 or more fluorine atoms. )
[ chemical 11]
(wherein R is 42 Represents an alkyl group which may be substituted with 1 or more fluorine atoms. )
As R 41 、R 42 Examples of the alkyl group of the "alkyl group which may be substituted with 1 or more fluorine atoms" include methyl, ethyl, propyl, butyl and the like. Among them, methyl, ethyl and tert-butyl are preferable, and methyl is more preferable.
Particularly preferred are the fluorinated acrylic monomers represented by the following formula.
[ chemical 12]
Specific examples of the fluorine-containing acrylic monomer represented by the above formula include methyl-2-fluoroacrylate and ethyl-2-fluoroacrylate.
The fluorinated acrylic monomer may be a monomer represented by the following formula (a monomer having a dicyclopentadienyl group represented by the above-mentioned formulas (I-1) and (I-2)). For example, by using these monomers, the dicyclopentenyl group represented by the above formulas (I-1) and (I-2) can be introduced into the copolymer.
[ chemical 13]
The above-mentioned fluorinated styrene monomer is preferably one which can introduce C-F bonds into the main chain of the polymer and can raise the glass transition temperature of the polymerSelected from CF 2 ＝CF-C 6 H 5 、CF 2 ＝CF-C 6 H 4 -CH 3 And CF (compact F) 2 ＝CF-C 6 H 4 -CF 3 At least 1 kind of the group consisting of the fluorinated styrene monomers shown in the following formula are preferable.
[ chemical 14]
The above-mentioned hydrofluoroolefin is preferably a material in which a hydrogen atom of ethylene is replaced with a fluorine atom, and examples thereof include fluoroethylene, trifluoroethylene, vinylidene fluoride [ VDF ], and the like. Among them, vinyl fluoride is preferable.
The fluorine-containing norbornene may have 1 norbornene skeleton or may have 2 or more norbornene skeletons as long as it has a polymerizable group. Fluorine-containing norbornene is produced by a Diels-Alder addition reaction of an unsaturated compound with a diene compound.
Examples of the unsaturated compound include fluoroolefins, fluoroallyl alcohol, fluorohomoallyl alcohol, α -fluoroacrylic acid, α -trifluoromethylacrylic acid, fluoroacrylate or fluoromethylacrylate, 2- (benzoyloxy) pentafluoropropane, 2- (methoxyethoxymethyloxy) pentafluoropropene, 2- (tetrahydroxypyranoxy) pentafluoropropene, 2- (benzoyloxy) trifluoroethylene, and 2- (methoxymethyloxy) trifluoroethylene.
As the diene compound, cyclopentadiene, cyclohexadiene, and the like can be exemplified.
Examples of the fluorine-containing norbornene include compounds represented by the following formula.
[ 15]
Among the above-mentioned fluorine-containing monomers, the above-mentioned fluorine-containing monomers preferably contain at least 1 selected from the group consisting of fluorine-containing ethylene, fluorine-containing propylene and fluorine-containing vinyl ether, more preferably contain at least 1 selected from the group consisting of vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene, fluorine ethylene, hexafluoropropylene and perfluoro (alkyl vinyl ether).
In addition, the fluorine-containing monomer preferably contains at least 1 of a compound represented by the following formula, tetrafluoroethylene, and hexafluoropropylene.
[ 16]
Further, the fluorine-containing monomer preferably contains at least 1 kind of compound represented by the following formula.
[ chemical 17]
When the polymer contains the fluorine-containing monomer unit, the fluorine-containing monomer unit is preferably 1 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, and further preferably 80 mol% or less, more preferably 50 mol% or less, still more preferably 30 mol% or less, with respect to the total of the polymerized units constituting the copolymer, because of excellent low dielectric constant and low dielectric loss tangent.
The copolymer of the present invention may contain the above-mentioned aromatic vinyl monomer unit, a monomer unit containing a crosslinking group, a monomer unit providing a homopolymer having a glass transition temperature of 150℃or higher, and "other monomer units" other than the fluorine-containing monomer unit (polymerization units based on other monomers).
Examples of the other monomer include a monomer containing no fluorine (hereinafter also referred to as "non-fluorine-containing monomer") which is reactive with the aromatic vinyl monomer, the monomer containing a crosslinking group, and the monomer providing a homopolymer having a glass transition temperature of 150 ℃ or higher. Examples of the non-fluorine-containing monomer include hydrocarbon monomers.
The other monomer unit (polymerized unit based on the other monomer) is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, still more preferably 1 mol% or more, and further preferably 50 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% or less, based on the total polymerized units constituting the copolymer, because of excellent low dielectric constant and low dielectric loss tangent.
Examples of the other monomer include:
olefins such as ethylene, propylene, butene, isobutylene and 1-decene;
alkyl vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether and 2-ethylhexyl vinyl ether;
vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl valerate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl versatate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl benzoate, vinyl p-tert-butylbenzoate, vinyl cyclohexane carboxylate, vinyl monochloroacetate, vinyl adipate, vinyl acrylate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl cinnamate, vinyl undecylenate, vinyl glycolate, vinyl hydroxy propionate, vinyl hydroxy butyrate, vinyl hydroxy valerate, vinyl hydroxy isobutyrate, vinyl hydroxy cyclohexane carboxylate, and the like;
Alkyl allyl ethers such as ethyl allyl ether, propyl allyl ether, butyl allyl ether, isobutyl allyl ether, and cyclohexyl allyl ether;
alkyl allyl esters such as ethyl allyl ester, propyl allyl ester, butyl allyl ester, isobutyl allyl ester, and cyclohexyl allyl ester; etc.
Among them, olefins and alkyl vinyl ethers are preferable, 1-decene, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether and 2-ethylhexyl vinyl ether are more preferable, and 1-decene, cyclohexyl vinyl ether and 2-ethylhexyl vinyl ether are still more preferable.
As the other monomer, a monomer having an alicyclic structure is preferably selected from the viewpoint of imparting solvent solubility to the copolymer.
The monomer having an alicyclic structure is preferably one or more (meth) acrylic esters selected from the group consisting of isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentanyl acrylate and dicyclopentanyl methacrylate.
The hydrocarbon monomer having a functional group may be used as the hydrocarbon monomer of the other monomer. Examples of the functional group-containing hydrocarbon monomer include OH group-containing monomers. Examples of the functional group-containing hydrocarbon monomer include:
Non-fluorine-containing monomers having an OH group (hydroxyl group) such as hydroxyalkyl vinyl ethers, e.g., hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyisobutyl vinyl ether, and hydroxycyclohexyl vinyl ether;
non-fluorine-containing monomers having a carboxyl group such as itaconic acid, succinic anhydride, fumaric acid, fumaric anhydride, crotonic acid, maleic anhydride, and bis 2-ethylhexyl fumarate;
glycidyl group-containing non-fluorine-containing monomers such as glycidyl vinyl ether and glycidyl allyl ether;
amino group-containing non-fluorine-containing monomers such as aminoalkyl vinyl ether and aminoalkyl allyl ether;
non-fluorine-containing monomers having an amide group such as (meth) acrylamide and methylolacrylamide; etc.
The copolymer of the present invention is preferably a thermosetting resin in view of its excellent low dielectric constant and low dielectric loss tangent. For example, a thermosetting resin can be provided by using the above aromatic vinyl monomer, a monomer containing a crosslinking group, and a monomer providing a homopolymer having a glass transition temperature of 150 ℃ or higher.
The fluorine content of the copolymer of the present invention is preferably 10 mass% or less, more preferably 5 mass% or less, still more preferably 3 mass% or less, based on the total mass of the copolymer, and may not contain fluorine.
The fluorine content of the copolymer can be determined by elemental analysis using an automatic sample combustion apparatus.
The number average molecular weight of the copolymer of the present invention is preferably 1000 to 50000. When the content is within this range, the solvent solubility and thermosetting properties are improved. The number average molecular weight of the fluorine-containing thermosetting resin is more preferably 2000 to 30000, and still more preferably 4000 to 20000.
The number average molecular weight of the above copolymer can be determined by Gel Permeation Chromatography (GPC).
The glass transition temperature of the copolymer of the present invention is preferably 140℃or higher, more preferably 150℃or higher, still more preferably 180℃or higher, still more preferably 200℃or higher, particularly preferably 220℃or higher, from the viewpoint of excellent electrical characteristics, particularly, the ability to lower the dielectric loss tangent. The higher the glass transition temperature is, the better, but from the viewpoint of processability, it is preferably 300℃or lower.
The above glass transition temperature is a value determined by the midpoint method according to the heat absorption in the second round using a DSC measuring device according to ASTM E1356-98 under the following conditions.
Measurement conditions
Heating rate: 20 ℃/min
Sample amount: 10mg of
Thermal cycling: -50-300 ℃, heating, cooling and heating
The heat curing temperature of the copolymer of the present invention is preferably 300℃or less, more preferably 270℃or less, still more preferably 250℃or less, particularly preferably 240℃or less, and most preferably 230℃or less, from the viewpoint of excellent low dielectric constant and low dielectric loss tangent. The lower limit is not particularly limited, but is preferably 80℃or higher, more preferably 100℃or higher.
The heat curing temperature is a value determined by the method described in examples described later.
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 examples below.
The copolymer of the present invention preferably has a dielectric constant (relative dielectric constant) of 2.50 or less, more preferably 2.47 or less, still more preferably 2.30 or less, and particularly preferably 2.25 or less, from the viewpoint of excellent low dielectric constant and low dielectric loss tangent. The lower limit is not particularly limited, and the smaller the value, the more preferable.
The dielectric constant (relative dielectric constant) is a value determined by the method described in examples described below.
The copolymer of the present invention preferably has a dielectric loss tangent of 0.0030 or less, more preferably 0.0028 or less, still more preferably 0.0025 or less, and particularly preferably 0.0020 or less, from the viewpoint of excellent low dielectric constant and low dielectric loss tangent. The lower limit is not particularly limited, and the smaller the value, the more preferable.
The dielectric loss tangent is a value determined by the method described in examples described below.
The copolymer of the present invention can be produced, for example, by a method for producing a copolymer comprising the steps of: the composition of the copolymer is appropriately adjusted as described above, and the aromatic vinyl monomer, the monomer containing a crosslinking group, and the monomer providing a homopolymer having a glass transition temperature of 150 ℃ or higher are polymerized in the presence of a chain transfer agent.
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 in polymerization, and among these, it is preferably obtained by a solution polymerization method.
The copolymer of the present invention is preferably produced by polymerizing the aromatic vinyl monomer, the monomer containing a crosslinking group, and the monomer providing a homopolymer having a glass transition temperature of 150 ℃ or higher by a solution polymerization method using an organic solvent, a polymerization initiator, a chain transfer agent, or the like in polymerization. The polymerization temperature is usually from 0 to 150The temperature is preferably 5 to 130 ℃. The polymerization pressure is usually 0.1MPaG to 10MPaG (1 kgf/cm) 2 G～100kgf/cm 2 G)。
The organic solvents include: esters such as methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, and t-butyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aliphatic hydrocarbons such as hexane, cyclohexane, octane, nonane, decane, undecane, dodecane, and mineral spirits; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha; alcohols such as methanol, ethanol, t-butanol, isopropanol, and ethylene glycol monoalkyl ether; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; dimethyl sulfoxide, or the like, or a mixture thereof, or the like.
As the polymerization initiator, persulfate salts such as ammonium persulfate and potassium persulfate (sodium bisulfite, sodium metabisulfite, cobalt naphthenate, dimethylaniline and other reducing agents may be used in combination as required); redox initiators comprising an oxidizing agent (e.g., ammonium peroxide, potassium peroxide, etc.) and a reducing agent (e.g., sodium sulfite, etc.) and a transition metal salt (e.g., ferric sulfate, etc.); diacyl peroxides such as acetyl peroxide, benzoyl peroxide, diisobutyryl peroxide, dilauroyl peroxide, didecanoyl peroxide, dicyclohexyl peroxydicarbonate, and bis (4-t-butylcyclohexyl) peroxydicarbonate; di-alkoxycarbonyl peroxides such as isopropoxycarbonyl peroxide and t-butoxycarbonyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; hydroperoxides such as hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, etc.; dialkyl peroxides such as di-t-butyl peroxide and dicumyl peroxide; alkyl peroxyesters such as t-butyl peroxyacetate, t-butyl peroxypivalate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxybenzoate, t-butyl peroxyneodecanoate, t-butyl peroxylaurate, t-hexyl peroxypivalate, t-hexyl peroxy-2-ethylhexanoate, t-hexyl peroxyisopropyl monocarbonate; azo compounds such as 2,2' -azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), 2' -azobis (2-methylpentanenitrile), 2' -azobis (2-cyclopropylpropionitrile), dimethyl 2,2' -azobisisobutyrate, 2' -azobis [2- (hydroxymethyl) propionitrile ], and 4,4' -azobis (4-cyanopentenoic acid).
As the chain transfer agent, for example, a thiol compound may be used in addition to such a compound as 2, 4-diphenyl-4-methyl-pentene. The thiol compound may be any thiol compound known to function as a chain transfer agent, and is preferably t-dodecyl mercaptan, n-dodecyl mercaptan, t-octyl mercaptan, n-octyl mercaptan, trimethylolpropane tri-3-mercaptopropionate, pentaerythritol tetra-3-mercaptopropionate, dipentaerythritol hexa-3-mercaptopropionate, or (tris- [ (3-mercaptopropionyloxy) -ethyl ] -isocyanurate). Among them, from the viewpoints of easiness of polymerization control and toughness of the resulting copolymer, it is particularly preferable to use monoalkyl mercaptans having 5 to 30 carbon atoms such as t-dodecyl mercaptan, n-dodecyl mercaptan, t-octyl mercaptan and n-octyl mercaptan.
In addition, for example, alcohols, preferably alcohols having 1 to 10 carbon atoms, and more preferably monohydric alcohols having 1 to 10 carbon atoms, can be used. Specifically, methanol, ethanol, propanol, isopropanol, n-butanol, t-butanol, 2-methylpropanol, cyclohexanol, methylcyclohexanol, cyclopentanol, methylcyclopentanol, dimethylcyclopentanol may be used. Among them, methanol, isopropanol, t-butanol, cyclohexanol, methylcyclohexanol, cyclopentanol, methylcyclopentanol, and the like are preferable, and methanol and isopropanol are particularly preferable.
Among them, 2, 4-diphenyl-4-methyl-pentene is preferable. For example, by combining a diene monomer containing an olefin having different reactivity such as a diene monomer having the above-mentioned dicyclopentadienyl group with 2, 4-diphenyl-4-methyl-pentene, gelation during polymerization can be prevented, and a crosslinkable group can be introduced in one stage.
The copolymer composition (resin composition) of the present invention contains the above copolymer and a solvent.
The copolymer composition of the present invention has the above-described structure, and is excellent in solvent solubility and thermosetting properties. In addition, the use of the resin layer makes it possible to provide the resin layer with a low dielectric constant and a low dielectric loss tangent.
In the copolymer composition of the present invention, the above-mentioned copolymer is the same as the copolymer of the present invention. Therefore, the preferable mode of the copolymer described in the copolymer of the present invention can be used in its entirety.
The copolymer composition of the present invention comprises a solvent. The solvent is preferably an organic solvent, and examples of the organic solvent include esters such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, and propylene glycol methyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; cyclic ethers such as tetrahydrofuran and dioxane; 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; mixed solvents thereof, and the like.
The copolymer composition of the present invention may further contain the above-mentioned monomer, other monomer components, for example, monomer components such as styrene, methyl (meth) acrylate, and the like.
From the aspect of improving thermosetting properties, the copolymer composition of the present invention may contain a crosslinking agent. The crosslinking agent used in the present embodiment is not particularly limited as long as it has 2 or more carbon-carbon unsaturated double bonds in the molecule. That is, the crosslinking agent may be formed by reacting with a copolymer of the aromatic vinyl monomer of the present invention, the monomer having a crosslinking group, and the monomer providing a homopolymer having a glass transition temperature of 150℃or higher, and curing the resultant. The crosslinking agent is preferably a compound having 2 or more carbon-carbon unsaturated double bonds at the terminal. The crosslinking agent may be used alone or in combination of 2 or more.
Specific examples of the crosslinking agent include trialkenyl isocyanurate compounds such as triallyl isocyanurate (TAIC), bismaleimides described later, divinylbenzene, dicyclopentenyl (meth) acrylate, monomer components containing 2 or more vinyl groups of pentaerythritol tri (meth) acrylate, vinyl compounds having 2 or more vinyl groups in the molecule such as polybutadiene, and the like. As the vinyl compound having 2 or more vinyl groups in the molecule, a polymer containing 2 or more vinyl groups such as polybutadiene is preferable. The copolymer composition of the present invention preferably contains: the polymer containing 2 or more vinyl groups or the monomer component containing 2 or more vinyl groups. From the viewpoint of improving thermosetting properties, bismaleimides are preferable. Preferred bismaleimides include, for example, 1, 2-bis (maleimide) ethane, N-succinimidyl-3-maleimide propionate, 4' -diphenylmethane bismaleimide, N ' -m-phenylene bismaleimide, N, N ' -p-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3' -dimethyl-5, 5' -diethyl-4, 4' -diphenylmethane bismaleimide, 4-methyl-1, 3-phenylene bismaleimide, 1,6' -bismaleimide- (2, 4-trimethyl) hexane, 1-maleimide-3-maleimidomethyl-3, 5-trimethylcyclohexane 1,1' - (cyclohexane-1, 3-diylbis (methylene)) bis (1H-pyrrole-2, 5-dione), 1' - (4, 4' -methylenebis (cyclohexane-4, 1-diyl)) bis (1H-pyrrole-2, 5-dione), 1' - (3, 3' - (piperazine-1, 4-diyl) bis (propane-3, 1-diyl)) bis (1H-pyrrole-2, 5-dione), 2' - (ethylenedioxy) bis (ethylmaleimide), succinimidyl-4- (N-maleimidomethyl) cyclohexane-1-carboxylate, 2, 2-bis [4- (4-maleimidophenoxy) phenyl ] propane, and the like.
For example, 1, 2-polybutadiene can be preferably used as the polybutadiene used in the present embodiment. Commercially available products may be used, and for example, liquid polybutadiene may be obtained from the company soyama, japan, in addition to JSR: product names B-1000, 2000, 3000. In addition, as a copolymer containing a 1, 2-polybutadiene structure that can be preferably used, "Ricon100" of TOTAL CRAY VALLEY company can be exemplified. As the maleimide used in the present embodiment, commercially available ones can be used, and for example, "BMI-2300" manufactured by Daikovia Kagaku Co., ltd., and "MIR-3000" manufactured by Japanese Kagaku Co., ltd., K. I Chemical Industry Co., LTD., "BMI-70" manufactured by K. I Chemical Industry Co., LTD., "BMI-80" manufactured by LTD may be preferably used.
The content of the maleimide group in the copolymer resin composition is not particularly limited, and may be appropriately set according to desired characteristics. The content of the maleimide compound is preferably 1 part by mass or more, more preferably 5 parts by mass or more, based on100 parts by mass of the copolymer solid component (resin solid component) in the copolymer composition. The upper limit is preferably 90 parts by mass or less, more preferably 60 parts by mass or less, still more preferably 40 parts by mass or less, and also 30 parts by mass or less. When the amount is within this range, the balance between the electrical characteristics and the curing reactivity tends to be good.
Only 1 kind of maleimide may be used, or 2 or more kinds may be used. When 2 or more kinds are used, the total amount is preferably within the above range.
Further, the polymerization initiator and photopolymerization initiator may be contained. Examples of the photopolymerization initiator include: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, and the like; acetophenones such as acetophenone, 2-diethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, 1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropane-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1-one; anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, and 2-pentylalnthraquinone; thioxanthones such as 2, 4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzil dimethyl ketal; benzophenone such as benzophenone, 4-benzoyl-4 '-methyldiphenyl sulfide, and 4,4' -dimethylaminobenzophenone; phosphine oxides such as 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide and bis (2, 4, 6-trimethylbenzoyl) -phenyl phosphine oxide.
These may be used alone or in combination of 2 or more.
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, in the case where the copolymer contains a dicyclopentadienyl group, self-crosslinking can be performed even without using a crosslinking agent or a curing accelerator. Therefore, it is not necessary to add an extra component, and the electrical characteristics can be improved.
In the copolymer composition of the present invention, the copolymer is preferably 10% by mass or more, more preferably 25% by mass or more, still more preferably 40% by mass or more, and may be 100% by mass or less, or may be 80% by mass or less, based on 100% by mass of the solid content.
The copolymer composition of the present invention may contain a flame retardant, an inorganic filler, a silane coupling agent, a release agent, a pigment, an emulsifier, and the like.
The copolymer composition of the present invention may contain various additives according to the desired characteristics. Examples of the additives include pigment dispersants, defoamers, leveling agents, UV absorbers, light stabilizers, thickeners, adhesion improvers, matting agents, and the like.
From the viewpoint of thermosetting, the gel fraction of the copolymer composition of the present invention is preferably 30% or more. The gel fraction is more preferably 35% or more, still more preferably 40% or more, particularly preferably 50% or more.
The gel fraction is a value measured by the method described in examples described below.
The method for producing the copolymer composition of the present invention is not particularly limited. Examples thereof include a method of mixing a solution or dispersion of the copolymer with other components.
The copolymer composition of the present invention can be suitably used as a resin layer of a laminate comprising a substrate and a resin layer provided on the substrate, and in particular, can be suitably used as a resin layer of a metal-clad laminate. In addition, the resin composition can be used for powder coating resins, resins for optical applications, and resist materials. The invention also relates to a film comprising the copolymer. The present invention also relates to a laminate comprising a base material and a resin layer provided on the base material, wherein the resin layer contains the copolymer.
The copolymer composition of the present invention is a metal-clad laminate comprising a metal foil and a resin layer provided on the metal foil, and the resin layer can be suitably used for a metal-clad laminate formed from the copolymer composition of the present invention. The resin layer can be formed by curing the copolymer composition of the present invention described above. 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 contains the copolymer.
The metal-clad laminate includes a metal foil and a resin layer. The resin layer has excellent insulation properties and functions as a base material for the metal-clad laminate.
As the metal foil, a metal foil composed of copper, aluminum, iron, nickel, chromium, molybdenum, tungsten, zinc, or an alloy thereof, preferably a copper foil, can be exemplified. In addition, for the purpose of improving the adhesion, a plate wall, nickel plating, copper zinc alloy plating, or chemical or mechanical surface treatment with aluminum alkoxide, aluminum chelate, silane coupling agent, or the like may be performed.
The metal-clad laminate may further include other layers as long as the metal foil and the resin layer are provided, and the metal foil and the resin layer may be each 1 kind or 2 or more kinds.
The metal-clad laminate may further include a second resin layer provided on the resin layer (hereinafter referred to as "first resin layer"). That is, the metal-clad laminate may be formed by laminating a metal foil, a first resin layer, and a second resin layer in this order. The first resin layer may function as an adhesive layer for bonding the metal foil to the second resin layer, in addition to the function as a base material.
In the metal-clad laminate, the first resin layer may be provided on a surface (surface on the opposite side) of the metal foil, which surface is different from the surface on which the first resin layer is provided. That is, the metal-clad laminate may be laminated in the order of the first resin layer, the metal foil, and the first resin layer, or may be laminated in the order of the first resin layer, the metal foil, the first resin layer, and the second resin layer.
The second resin layer may be a resin used in a conventional printed circuit board, and is preferably at least 1 resin selected from the group consisting of polyethylene terephthalate and polyimide, and more preferably polyimide from the viewpoint of heat resistance.
As the first resin layer, a film having a thickness of 1 μm to 150 μm can be used. In the case where the metal foil is bonded to the second adhesive layer through the first resin layer, the thickness of the first resin layer after drying may be 1 μm to 100 μm.
As the second resin layer, a resin film having a thickness of 1 μm to 150 μm can be used.
The metal-clad laminate can be obtained by a production method comprising the steps of: a metal-clad laminate is obtained by bonding a metal foil to a film comprising the copolymer composition.
The method of bonding is preferably a method of laminating a metal foil and a film comprising the copolymer composition and then thermocompression bonding the laminated film at 50 to 300 ℃.
The production method may further include a step of molding the copolymer composition to obtain a film composed of the copolymer.
The molding method includes, but is not particularly limited to, a melt extrusion molding method, a solvent casting method, a spray method, and the like. The copolymer composition may contain an organic solvent, a curing agent, etc., and may also contain a curing accelerator, a pigment dispersant, a defoaming agent, a leveling agent, a UV absorber, a light stabilizer, a thickener, an adhesion improver, a matting agent, etc.
The metal-clad laminate may be obtained by a production method including a step of forming a first resin layer by coating the copolymer composition on a metal foil.
The manufacturing method may include the following steps after the step of forming the first resin layer: further, a resin film to be a second resin layer is bonded to the first resin layer, thereby obtaining a metal-clad laminate including a metal foil and the first and second resin layers. As the resin film, a film made of a resin suitable for forming the second resin layer can be given.
As a method for bonding the resin film, a method of thermocompression bonding at 50 to 300℃using a heated press is preferable.
Among the above-mentioned production methods, examples of the method of applying the composition for forming the first resin layer to the metal foil include brushing, dipping, spraying, comma, doctor blade, die, lip, roll coater, curtain coater, and the like. After the composition is applied, the composition may be dried at 25 to 200℃for 1 minute to 1 week by a hot air drying oven or the like to be cured.
The metal-clad laminate may be produced by a production method comprising the steps of: a step of forming a first resin layer by applying the copolymer composition to a resin film serving as a second resin layer; and a step of adhering a metal foil to the first resin layer of the laminate composed of the first resin layer and the second resin layer obtained in the forming step, thereby obtaining a metal-clad laminate including the metal foil and the first and second resin layers. The resin film may be a film made of a resin suitable for forming the second resin layer.
Examples of the method of applying the composition for forming the first resin layer to the resin film include brushing, dipping, spraying, comma, doctor blade, die, lip, roll coater, curtain coating, and the like. After the composition is applied, the composition may be dried at 25 to 200℃for 1 minute to 1 week by a hot air drying oven or the like to be cured.
In the above-described production method, the metal foil is preferably bonded to the first resin layer of the laminate composed of the first resin layer and the second resin layer by the following method: a laminate composed of a first resin layer and a second resin layer is laminated on a metal foil so that the first resin layer of the laminate is bonded to the metal foil, and then the laminate is thermally bonded by a heated press at 50-300 ℃.
The metal-clad laminate can be applied to a printed board having a pattern circuit formed by etching a 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 printed board may be a flexible board or a rigid board, but is preferably a rigid board.
The printed board may include a cover film on the metal-clad laminate, and the cover film may be bonded to the metal-clad laminate via the resin layer.
The etching method is not limited, and any conventionally known method can be used. The pattern circuit is not limited, and may be a printed circuit board of any pattern circuit.
The application of the printed circuit board is not limited. For example, the printed circuit board has a resin layer having a low dielectric constant and a low dielectric loss tangent, and thus can be used for a printed circuit board used in applications having a high frequency band such as 4G (37.5 Mbps) and 5G (several G to 20 Gbps).
Examples
The present invention will be described with reference to examples, but the present invention is not limited to the examples.
The present invention will be described more specifically with reference to examples.
The physical properties described in the present specification were measured by the following measurement methods.
(1) NMR analysis
Measurement device: NMR measuring apparatus manufactured by VARIAN Co
1H-NMR measurement conditions: 400MHz (tetramethylsilane=0 ppm)
(2) Elemental analysis (determination of fluorine content (% by mass))
Measurement device: an automatic sample burner (AQF-100 manufactured by Mitsubishi chemical Co., ltd.) was incorporated in ion chromatography (ICS-1500 Ion Chromatography System manufactured by DIONEX Co., ltd.)
Sample 3mg
(3) Molecular weight
Measurement device: shodex GPC-104 manufactured by Showa Denko Co., ltd
Measurement conditions: tetrahydrofuran was used as eluent, and polystyrene of known molecular weight was used as a standard sample of molecular weight.
(4) Glass transition temperature
The glass transition temperature and the crystalline melting point were determined by the mid-point method from the heat absorption in the second round using a DSC measurement apparatus made by METRER TOLEDO according to ASTM E1356-98.
Measurement conditions
Heating rate: 20 ℃/min
Sample amount: 10mg of
Thermal cycling: -50-300 ℃, heating, cooling and heating
(5) Relative permittivity and dielectric loss tangent
The copolymer film produced in the synthesis example was subjected to vacuum hot pressing. The relative permittivity and dielectric loss tangent of the film (sample F) thus produced were measured as follows.
The resonance frequency and the change in Q value of the sample F produced above were measured with a cavity resonator using a network analyzer, and the dielectric loss tangent (tan δ) at 12GHz was calculated according to the following formula. The cavity resonator method was performed according to the teaching of the university of Jade, proprietary [ non-destructive measurement of complex dielectric constants of dielectric plate materials based on the cavity resonator method MW87-53 ].
tanδ＝(1/Qu)×{1+(W2/W1)}-(Pc/ωW1)
[ number 1]
XtanX＝(L/2M)YcosY
P c ＝P 1 +P 2 +P 3
Wherein the symbols in the formula are as follows.
D: diameter of cavity resonator (mm)
M: single side length (mm) of cavity resonator
L: sample length (mm)
c: light velocity (m/s)
Id: attenuation (dB)
F0: resonant frequency (Hz)
F1: high frequency (Hz) with 3dB attenuation from resonance point
F2: low frequency (Hz) with 3dB attenuation from the resonance point
ε 0: vacuum dielectric constant (H/m)
εr: relative permittivity of sample
Mu 0: vacuum magnetic permeability (H/m)
Rs: effective surface resistance (Ω) taking into account the surface roughness of the conductor cavity
J0：-0.402759
J1：3.83171
(6) Evaluation of solvent solubility
For 20g of the copolymer produced in the synthesis example, 30g of methyl ethyl ketone was weighed into a 100ml sample bottle, and mixed by shaking, and the solubility was visually confirmed.
(7) Evaluation of thermosetting Property (gel fraction)
The solution prepared in the above evaluation of solvent solubility or the cured composition using the copolymer and the crosslinking agent was put in an aluminum cup in an amount of 2g, and heated and dried at each set firing temperature for 1 hour to obtain a heat-cured product. The solidified product was taken out and wrapped with 400 mesh wire gauze weighed in advance. To a 50ml sample tube, 25ml of methyl ethyl ketone and a solidified material covered with a metal mesh were added, and the solidified material was immersed in methyl ethyl ketone for 24 hours. Then, the metal mesh was taken out and dried, and the mass after drying was measured to calculate the mass of the dried cured product after impregnation with methyl ethyl ketone.
The gel fraction was calculated as mass of dried cured product after methyl ethyl ketone impregnation/mass of cured product before methyl ethyl ketone impregnation×100.
(8) Heat curing temperature
The heat curing temperature was the temperature of the peak top of the exothermic peak observed when the measurement was performed by a DSC measuring device, or 10mg of the sample was warmed from room temperature at a warming rate of 10℃per minute by using a differential thermal/thermogravimetric measuring device [ TG-DTA ] (trade name: TG/DTA7200, manufactured by Hitachi high technology Co., ltd.) and the temperature of the peak top of the exothermic peak observed in a temperature region where the weight was reduced by less than 1% was taken as the heat curing temperature.
(9) Linear expansion coefficient
The film (sample piece) of the copolymer produced in the synthesis example was produced, and the linear expansion coefficient (linear expansion coefficient) was measured as follows.
The linear expansion coefficient of the film was obtained by performing TMA measurement in the following compression mode using TMA-7100 (manufactured by hitachi high technology corporation).
[ measurement of stretching mode ]
As a sample sheet, an extruded film having a thickness of 760 μm and cut to a length of 10mm and a width of 10mm was used, and the linear expansion coefficient was determined from the displacement of the sample at 30℃to 200℃at a heating rate of 2℃per minute while compressing the film under a load of 49 mN.
< Synthesis of copolymer >
Synthesis example 1
Into a 300ml four-necked flask, 100g of methyl isobutyl ketone, 16g of styrene, 24g of dicyclopentenyl vinyl ether, 24g of cyclohexylmaleimide (glass transition temperature of homopolymer: 300 ℃ C.) and 0.8g of 2, 4-diphenyl-4-methyl-1-pentene were charged. The internal temperature was set at 70℃and 2g of t-butyl peroxypivalate was added thereto to react for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate the copolymer. The copolymer thus obtained was washed with methanol, filtered and dried to obtain a copolymer.
According to NMR analysis, the composition of the resulting copolymer was: the structure derived from styrene was 41 mol%, the structure derived from dicyclopentenyl vinyl ether was 15 mol%, and the structure derived from cyclohexylmaleimide was 44 mol%.
According to 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 ℃.
As a result of DSC measurement to 250 ℃, a peak of heat release was confirmed from around 190℃to 250 ℃.
Synthesis example 2
Into a 300ml four-necked flask, 60g of methyl isobutyl ketone, 11g of styrene, 14g of dicyclopentadiene, and 5g of cyclohexylmaleimide were charged. The internal temperature was set at 90℃and 2g of t-butyl peroxy-2-ethylhexanoate was added thereto to react for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate the copolymer. The copolymer thus obtained was washed with methanol, filtered and dried to obtain a copolymer.
Based on elemental analysis and NMR analysis, the composition of the resulting copolymer was: the structure derived from styrene was 60 mol%, the structure derived from dicyclopentadiene was 6 mol%, and the structure derived from cyclohexylmaleimide was 34 mol%.
According to molecular weight analysis, the number average molecular weight (Mn) was 14000, and the weight average molecular weight (Mw) was 31000. The glass transition temperature (Tg) was 145 ℃.
(as a result of DSC measurement to 200 ℃, no peak of heat release was confirmed).
Synthesis example 3
Into a 300ml four-necked flask, 95g of methyl isobutyl ketone, 12g of styrene, 15g of dicyclopentadiene, 20g of cyclohexylmaleimide, 18g of 1, 2-trifluorovinylbenzene and 4g of 2, 4-diphenyl-4-methyl-1-pentene were charged. The internal temperature was set at 70℃and 2g of t-butyl peroxypivalate was added thereto to react for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate the copolymer. The copolymer thus obtained was washed with methanol, filtered and dried to obtain a copolymer.
Based on elemental analysis and NMR analysis, the composition of the resulting copolymer was: the structure derived from 1, 2-trifluoroethylbenzene (trifluorostyrene) was 6 mol%, the structure derived from styrene was 59 mol%, the structure derived from dicyclopentadiene was 5 mol%, and the structure derived from cyclohexylmaleimide was 30 mol%.
According to molecular weight analysis, the number average molecular weight (Mn) was 14000 and the weight average molecular weight (Mw) was 34000. The glass transition temperature (Tg) was 161 ℃. As a result of the elemental analysis, the fluorine content was 3.4 mass%.
As a result of DSC measurement to 200 ℃, a peak of heat release was confirmed in the vicinity of 170℃to 200 ℃.
Synthesis example 4
Into a 300ml four-necked flask, 100g of methyl isobutyl ketone, 35g of dicyclopentenyl vinyl ether, 18g of cyclohexylmaleimide and 2g of 2, 4-diphenyl-4-methyl-1-pentene were charged. The internal temperature was set at 70℃and 1g of t-butyl peroxy-2-ethylhexanoate was added thereto to react for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate the copolymer. The copolymer thus obtained was washed with methanol, filtered and dried to obtain a copolymer.
Based on elemental analysis and NMR analysis, the composition of the resulting copolymer was: the structure derived from the dicyclopentenyl vinyl ether was 46 mol% and the structure derived from the cyclohexylmaleimide was 54 mol%.
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 ℃.
As a result of the DSC measurement, a peak of heat release was confirmed from 160℃to 240 ℃.
Synthesis example 5
Into a 300ml four-necked flask, 100g of methyl isobutyl ketone, 29g of dicyclopentadiene, 18g of cyclohexylmaleimide and 2g of 2, 4-diphenyl-4-methyl-1-pentene were charged. The internal temperature was set at 70℃and 1g of t-butyl peroxypivalate was added thereto to react for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate the copolymer. The copolymer thus obtained was washed with methanol, filtered and dried to obtain a copolymer.
Based on elemental analysis and NMR analysis, the composition of the resulting copolymer was: the structure derived from dicyclopentadiene was 36 mol%, and the structure derived from cyclohexylmaleimide was 64 mol%.
According to 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 ℃.
As a result of DSC measurement to 220 ℃, exothermic peaks were confirmed in the vicinity of 180℃to 220 ℃.
The polymers produced in Synthesis examples 1 to 5 and films of the copolymers produced using the polymers were measured and evaluated for polymer composition, physical properties, and the like, and the results are shown in Table 1.
The gel fraction of the polymers produced in Synthesis examples 1 to 5 was measured for the cured products produced at the firing temperatures shown in Table 1. The results are set forth in Table 1.
< preparation of copolymer composition >
According to the proportions shown in Table 2, cured compositions were prepared in which a solution of crosslinking agent A (an acetone solution of 4,4 '-diphenylmethane bismaleimide (concentration: 3 mass%) or a solution of crosslinking agent B (a methyl ethyl ketone solution of N, N' - (2, 4-trimethylhexane-1, 6-diyl) bismaleimide (concentration: 10 mass%) was mixed with a solution of MEK (methyl isobutyl ketone) of the polymers prepared in Synthesis examples 1 to 3 (concentration of solid content: 40 mass% (polymer solution)). The prepared compositions were fired at firing temperatures shown in table 2 to obtain cured products, and gel fractions thereof were measured. The results are set forth in Table 2.
TABLE 2
From table 2, it was confirmed that the curing temperature can be lowered by adding the crosslinking agent.
< Synthesis of copolymer >
Synthesis example 6
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 6 parts by mass of bis 2-ethylhexyl fumarate were put into a 300ml four-necked flask. The internal temperature was set at 85℃and 0.4 part by mass of t-butyl peroxy-2-ethylhexanoate was added thereto to react for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate the copolymer. The copolymer thus obtained was washed with methanol, filtered and dried to obtain a copolymer.
According to NMR analysis, the composition of the resulting copolymer was: the structure derived from styrene was 30 mol%, the structure derived from dicyclopentenyl vinyl ether was 11 mol%, the structure derived from cyclohexylmaleimide was 56 mol%, and the structure derived from bis 2-ethylhexyl fumarate was 3 mol%.
According to molecular weight analysis, the number average molecular weight (Mn) was 25728 and the weight average molecular weight (Mw) was 187116. The glass transition temperature (Tg) was 205 ℃.
As a result of TG-DTA measurement to 600℃an exothermic peak was confirmed at around 190℃to 250 ℃.
Synthesis example 7
120 parts by mass of methyl isobutyl ketone, 23 parts by mass of styrene, 40 parts by mass of cyclohexylmaleimide, 13 parts by mass of dicyclopentadiene, and 6 parts by mass of bis 2-ethylhexyl fumarate were put into a 300ml four-necked flask. The internal temperature was set at 85℃and 0.4 part by mass of t-butyl peroxy-2-ethylhexanoate was added thereto to react for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate the copolymer. The copolymer thus obtained was washed with methanol, filtered and dried to obtain a copolymer.
According to NMR analysis, the composition of the resulting copolymer was: the structure derived from styrene was 40 mol%, the structure derived from dicyclopentadiene was 5 mol%, the structure derived from cyclohexylmaleimide was 52 mol%, and the structure derived from bis 2-ethylhexyl fumarate was 3 mol%.
According to molecular weight analysis, the number average molecular weight (Mn) was 29862 and the weight average molecular weight (Mw) was 89407. The glass transition temperature (Tg) was 190 ℃.
As a result of TG-DTA measurement to 600℃an exothermic peak was confirmed at around 190℃to 250 ℃.
Synthesis example 8
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, 6 parts by mass of bis 2-ethylhexyl fumarate and 9 parts by mass of trifluorostyrene were charged into a 300ml four-necked flask. The internal temperature was set at 85℃and 0.2 parts by mass of t-butyl peroxy-2-ethylhexanoate was added thereto to react for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate the copolymer. The copolymer thus obtained was washed with methanol, filtered and dried to obtain a copolymer.
According to NMR analysis, the composition of the resulting copolymer was: 3 mol% of a structure derived from trifluorostyrene, 33 mol% of a structure derived from styrene, 9 mol% of a structure derived from dicyclopentenyl vinyl ether, 52 mol% of a structure derived from cyclohexylmaleimide, and 3 mol% of a structure derived from bis 2-ethylhexyl fumarate.
According to molecular weight analysis, the number average molecular weight (Mn) was 38829 and the weight average molecular weight (Mw) was 249053. The glass transition temperature (Tg) was 195 ℃.
As a result of TG-DTA measurement to 600℃an exothermic peak was confirmed at around 190℃to 250 ℃.
Synthesis example 9
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 and 10 parts by mass of 1-decene were put into a 300ml four-necked flask. The internal temperature was set at 85℃and 0.2 parts by mass of t-butyl peroxy-2-ethylhexanoate was added thereto to react for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate the copolymer. The copolymer thus obtained was washed with methanol, filtered and dried to obtain a copolymer.
According to NMR analysis, the composition of the resulting copolymer was: the structure derived from styrene was 16 mol%, the structure derived from dicyclopentadiene was 8 mol%, the structure derived from cyclohexylmaleimide was 66 mol%, and the structure derived from 1-decene was 10 mol%.
According to molecular weight analysis, the number average molecular weight (Mn) was 26910 and the weight average molecular weight (Mw) was 86654. The glass transition temperature (Tg) was 227 ℃.
As a result of TG-DTA measurement to 600℃an exothermic peak was confirmed at around 190℃to 250 ℃.
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 300ml four-necked flask. The internal temperature was set at 85℃and 0.2 parts by mass of t-butyl peroxy-2-ethylhexanoate was added thereto to react for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate the copolymer. The copolymer thus obtained was washed with methanol, filtered and dried to obtain a copolymer.
According to NMR analysis, the composition of the resulting copolymer was: the structure derived from styrene was 32 mol%, the structure derived from dicyclopentadiene was 5 mol%, the structure derived from cyclohexylmaleimide was 58 mol%, and the structure derived from limonene was 5 mol%.
According to molecular weight analysis, the number average molecular weight (Mn) was 22677 and the weight average molecular weight (Mw) was 85014. The glass transition temperature (Tg) was 220 ℃.
As a result of TG-DTA measurement to 600℃an exothermic peak was confirmed at around 190℃to 250 ℃.
Synthesis example 11
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 2-ethylhexyl vinyl ether were put into a 300ml four-necked flask. The internal temperature was set at 85℃and 0.2 parts by mass of t-butyl peroxy-2-ethylhexanoate was added thereto to react for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate the copolymer. The copolymer thus obtained was washed with methanol, filtered and dried to obtain a copolymer.
According to NMR analysis, the composition of the resulting copolymer was: the structure derived from styrene was 34 mol%, the structure derived from dicyclopentadiene was 4 mol%, the structure derived from cyclohexylmaleimide was 56 mol%, and the structure derived from 2-ethylhexyl vinyl ether was 6 mol%.
According to molecular weight analysis, the number average molecular weight (Mn) was 5665 and the weight average molecular weight (Mw) was 10242. The glass transition temperature (Tg) was 206 ℃.
As a result of TG-DTA measurement to 600℃an exothermic peak was confirmed at around 190℃to 250 ℃.
Synthesis example 12
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 and 10.3 parts by mass of N-dodecylmaleimide were put into a 300ml four-necked flask. The internal temperature was set at 85℃and 0.2 parts by mass of t-butyl peroxy-2-ethylhexanoate was added thereto to react for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate the copolymer. The copolymer thus obtained was washed with methanol, filtered and dried to obtain a copolymer.
According to NMR analysis, the composition of the resulting copolymer was: the structure derived from styrene was 43 mol%, the structure derived from dicyclopentadiene was 4 mol%, the structure derived from cyclohexylmaleimide was 43 mol%, and the structure derived from N-dodecylmaleimide was 10 mol%.
According to molecular weight analysis, the number average molecular weight (Mn) was 35618 and the weight average molecular weight (Mw) was 124375. The glass transition temperature (Tg) was 162 ℃.
As a result of TG-DTA measurement to 600℃an exothermic peak was confirmed at around 170℃to 250 ℃.
Synthesis example 13
Into a 300ml four-necked flask, 100 parts by mass of methyl isobutyl ketone, 16.2 parts by mass of styrene, 25.3 parts by mass of N-benzyl maleimide, 12 parts by mass of dicyclopentadiene and 2.5 parts by mass of 1-decene were charged. The internal temperature was set at 85℃and 0.2 parts by mass of t-butyl peroxy-2-ethylhexanoate was added thereto to react for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate the copolymer. The copolymer thus obtained was washed with methanol, filtered and dried to obtain a copolymer.
According to NMR analysis, the composition of the resulting copolymer was: the structure derived from styrene was 41 mol%, the structure derived from dicyclopentadiene was 3 mol%, the structure derived from N-benzyl maleimide was 52 mol%, and the structure derived from 1-decene was 4 mol%.
According to molecular weight analysis, the number average molecular weight (Mn) was 24540 and the weight average molecular weight (Mw) was 98036. The glass transition temperature (Tg) was 162 ℃.
As a result of TG-DTA measurement to 600℃an exothermic peak was confirmed at around 170℃to 250 ℃.
The polymer compositions, physical properties, and the like of the polymers produced in Synthesis examples 6 to 13 and films of the copolymers produced using the polymers were measured and evaluated, and the results are shown in Table 3.
The gel fraction of the polymers produced in synthesis examples 6 to 13 was measured for the cured products produced at the firing temperatures shown in table 3. The results are set forth in Table 3.
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 Sedan Co., ltd.) and 0.1 part by mass of an initiator (PERCUMYL D-40, manufactured by Nippon fat Co., ltd.) were dissolved in 48 parts by mass of methyl isobutyl ketone to prepare a copolymer composition.
The obtained copolymer composition was impregnated into a glass cloth, and then dried by heating at 100℃for about 3 minutes, whereby a prepreg was produced. Specifically, the glass cloth was #1035 glass (density: 2.6 g/cm) 3 Every 1m 2 Is prepared from the following components in parts by weight: 29.1g, glass cloth thickness measurement: measurement of relative permittivity of 29 μm: 2.66 dielectric loss tangent measurement: 0.0048). At this time, the content (resin content) of the copolymer composition was adjusted to about 40 mass%.
Next, 4 sheets of the produced prepregs were stacked, and heated and pressurized at a temperature of 250 ℃ and a pressure of 2.44MPa (megapascals) for 120 minutes to produce test pieces. The thickness of the test piece was 132.2. Mu.m. The relative permittivity and dielectric loss tangent of the test piece were measured, and as a result, the relative permittivity was 3.37, the dielectric loss tangent was 0.00522, and the gel fraction was 67%. The relative permittivity and the dielectric loss tangent of the cured polymer were calculated from the measured values of the relative permittivity and the dielectric loss tangent of the test body by the following formula, and as a result, the relative permittivity was 2.55 and the dielectric loss tangent was 0.00145.
Test body dielectric loss tangent=glass cloth wire dielectric loss tangent×glass cloth vol%/100+cured polymer dielectric loss tangent×cured polymer vol%/100
Glass cloth dielectric loss tangent=glass cloth wire dielectric loss tangent×glass cloth wire vol%/100+air dielectric loss tangent×air vol%/100
Glass cloth vol% = glass cloth per 1m 2 Weight/glass cloth density/thickness of prepreg per 1 sheet in test body after impregnation
Cured polymer vol% = 1-glass cloth vol%.

Claims (23)

1. A copolymer, comprising: an aromatic vinyl monomer unit, a monomer unit containing a crosslinking group, and a monomer unit providing a homopolymer having a glass transition temperature of 150 ℃ or higher.
2. The copolymer according to claim 1, which is a thermosetting resin.
3. The copolymer according to claim 1 or 2, wherein the aromatic vinyl monomer unit is a styrene unit.
4. A copolymer according to any one of claims 1 to 3, wherein the monomer unit containing a crosslinking group comprises a diene monomer unit having an alicyclic structure.
5. A copolymer according to any one of claims 1 to 3, wherein the monomer unit containing a crosslinking group comprises a monomer unit having a dicyclopentenyl structure.
6. A copolymer according to any one of claims 1 to 3, wherein the monomer units containing a crosslinking group comprise at least 1 selected from the group consisting of dicyclopentadiene units and dicyclopentenyl vinyl ether units.
7. The copolymer according to any one of claims 1 to 6, wherein the monomer unit providing a homopolymer having a glass transition temperature of 150 ℃ or higher comprises a maleimide-based unit.
8. The copolymer according to claim 7, wherein the maleimide-based unit comprises at least 1 selected from the group consisting of an N-cyclohexylmaleimide unit and an N-phenylmaleimide unit.
9. The copolymer of any one of claims 1 to 8, further comprising a fluoromonomer unit providing a C-F bond to the backbone.
10. The copolymer according to any one of claims 1 to 9, which has a glass transition temperature of 140 ℃ or higher.
11. The copolymer according to any one of claims 2 to 10, which has a heat curing temperature of 240 ℃ or less.
12. The copolymer according to any one of claims 1 to 11, which has solubility in methyl ethyl ketone or toluene.
13. 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 of the polymerized units constituting the copolymer.
14. The copolymer according to any one of claims 1 to 13, wherein the monomer unit providing a homopolymer having a glass transition temperature of 150 ℃ or higher is 5 mol% or more with respect to all the polymerized units constituting the copolymer.
15. The copolymer according to any one of claims 1 to 14, which has a dielectric loss tangent of 0.0030 or less.
16. A copolymer composition comprising the copolymer of any one of claims 1-15 and a solvent.
17. The copolymer composition of claim 16, comprising: a polymer containing 2 or more vinyl groups or a monomer component containing 2 or more vinyl groups.
18. The copolymer composition according to claim 16 or 17, which contains a photopolymerization initiator.
19. The copolymer composition according to any one of claims 16 to 18, having a gel fraction of 30% or more.
20. A film comprising the copolymer of any one of claims 1-15.
21. A laminate comprising a substrate and a resin layer provided on the substrate, wherein the resin layer comprises the copolymer according to any one of claims 1 to 15.
22. A metal-clad laminate comprising a metal foil and a resin layer provided on the metal foil, wherein the resin layer comprises the copolymer according to any one of claims 1 to 15.
23. A printed circuit board comprising a pattern circuit formed by etching the metal foil of the metal-clad laminate according to claim 22.
CN202280054502.5A 2021-08-17 2022-08-04 Copolymer and resin composition Pending CN117897416A (en)

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JP2022-108931 2022-07-06
JP2022108931A JP7339576B2 (en) 2021-08-17 2022-07-06 Copolymer and resin composition
PCT/JP2022/029967 WO2023022010A1 (en) 2021-08-17 2022-08-04 Copolymer and resin composition

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