Patent Application
20250043043
The present disclosure relates to a curable polymer, a curable composition, a prepreg, a multilayer body, a metal clad laminate and a wiring board.
A wiring board (also referred to as a printed wiring board) is used in applications such as electrical and electronic devices. The wiring board can be manufactured, for example, as follows: A curable composition including a curable polymer, and, if necessary, additive(s) such as a flame retardant and an inorganic filler (also referred to as filler.) is impregnated into a fibrous substrate, and the curable composition is (semi-)cured to produce a prepreg. One or more prepreg(s) are sandwiched between a pair of metal foils, and the resulting first temporary multilayer body is heated and pressed to produce a metal clad laminate. The metal foil on the outermost surface of the metal clad laminate is used to form a conductive pattern (also referred to as a circuit pattern) of wiring or the like. The outermost metal foil may be arranged only on one side of the first temporary multilayer body.
One or more prepreg(s) are further stacked on the resulting wiring board, which is sandwiched between a pair of metal foils, and the obtained second temporary multilayer body is heated and pressed to form a conductive pattern of wiring or the like using the metal foil on the outermost surface, thereby manufacturing a multilayer wiring board (also referred to as a multilayer printed wiring board). The outermost metal foil may be arranged only on one side of the second temporary multilayer body.
The heat-pressed product of the prepreg includes a fibrous substrate, a resin and an inorganic filler and is also referred to as a composite substrate. The composite substrate in the wiring board functions as an insulating layer.
The resin contained in the prepreg is a (semi-)cured product of the curable composition, and the resin contained in the composite substrate is a cured product of the curable composition.
Conventionally, a modified polyphenylene ether (modified PPE) oligomer (see formula (PPE-o) below.) having a polymerizable functional group at each of both ends has been widely used as a curable polymer for a prepreg used in production of a wiring board.
In recent applications such as portable electronic devices, signals have become increasingly high-frequency as higher speeds and larger capacities of communication have been achieved. A wiring board used in such applications is required to have a reduced transmission loss in a high-frequency region, which mainly includes a conductor loss caused by the surface resistance of metal foil and a dielectric loss cause by the dielectric dissipation factor (Df) of the composite substrate. For this reason, the resin contained in the composite substrate for the wiring board used in the above applications is required to have reduced dielectric loss in the high-frequency region. The dielectric dissipation factor (Df) generally depends on frequency. Given the same material, the higher the frequency, the larger the dielectric dissipation factor (Df) tends to be. The resin contained in the composite substrate preferably has a low dielectric dissipation factor (Df) under high-frequency condition.
The dielectric dissipation factor (Df) at 10 GHz of a polyphenylene ether (PPE) resin as a cured product of the modified polyphenylene ether (modified PPE) oligomer is around 0.002 to 0.003.
It is believed that higher speeds and larger capacities of communication are hereafter increasingly achieved, and it is believed that there is a need for a material capable of more reducing the dielectric dissipation factor (Df) under high-frequency conditions of a resin included in a composite substrate.
The wiring board may be used in a relatively high-temperature environment. Even in this case, in order to ensure the reliability of the wiring board, the resin contained in the prepreg and the composite substrate preferably has a sufficiently high glass transition temperature (Tg).
The present inventors have performed material development under the assumption that a resin containing no polar atoms in a main chain can more reduce the dielectric dissipation factor (Df) under high-frequency conditions than a PPE resin containing oxygen atoms as polar atoms in a main chain. As a result, the present inventors have invented a curable polymer which is suitable for a prepreg used in production of a wiring board and capable of producing a resin with lower dielectric dissipation factor (Df) under high-frequency conditions. It has been found that the composite substrate obtained using the curable composition containing the curable polymer has an effectively reduced dielectric dissipation factor (Df) under high-frequency conditions, a sufficiently high glass transition temperature (Tg), and good properties for use as a wiring board in a high-frequency region.
Related art of the present disclosure includes Japanese Unexamined Patent Application Publication No. S60-90205.
In this Literature, there is disclosed a method for producing a homopolymer of a vinylsilyl group-containing styrene compound represented by the following formula (I) (claim 1):
in which R1 and R2 are each an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and n is a number of 0 to 3.
In the above Literature, there is no description for applications of a prepreg, a metal clad laminate, and a wiring board, and no description for its dielectric properties. In the above Literature, there is no description for a copolymer of a vinylsilyl group-containing styrene compound represented by formula (I).
The present disclosure has been made in view of the above circumstances, and an object thereof is to provide a curable polymer capable of producing a resin with effectively reduced dielectric dissipation factor (Df) under high-frequency conditions and sufficiently high glass transition temperature (Tg), and a curable composition containing the same.
The present disclosure provides the following curable polymer, curable composition, prepreg, multilayer body, metal clad laminate and wiring board.
in which R1 and R2 each independently represent a hydrogen atom, a hydroxyl group or an organic group; the benzene ring optionally has a substituent other than the substituent in the above formula; and n is an integer of 0 or more.
in which R1 and R2 each independently represent a hydrogen atom, a hydroxyl group or an organic group; the benzene ring optionally has a substituent other than the substituent in the above formula; and n is an integer of 0 or more.
The present disclosure can provide a curable polymer capable of producing a resin with effectively reduced dielectric dissipation factor (Df) under high-frequency conditions and sufficiently high glass transition temperature (Tg), and a curable composition containing the same.
The above and other objects, features and advantages of the present disclosure will become more fully understood from the detailed description given hereinbelow and the accompanying drawings.
As used herein, (semi-)curing is a general term for semi-curing and curing.
As used herein the term “wiring board” includes a multilayer wiring board unless otherwise specified.
As used herein, the “polymer” encompasses a homopolymer and a copolymer, unless otherwise specified.
As used herein, the “alkyl group having 3 or more carbon atoms” may be linear or branched, unless otherwise specified.
As used herein, a compound whose isomers are present encompasses all such isomers, unless otherwise specified.
As used herein, the “weight average molecular weight (Mw)” means the weight average molecular weight in terms of standard polystyrene obtained by a gel permeation chromatography (GPC) method, and the “number average molecular weight (Mn)” means the number average molecular weight in terms of polystyrene obtained by a gel permeation chromatography (GPC) method, unless otherwise specified.
As used herein, Me represents a methyl group, Et represents an ethyl group, and Ph represents a phenyl group in any chemical formula.
As used herein, the term “high-frequency region” is defined as a region with a frequency of 1 GHz or higher.
As used herein, the term “to” indicating a numerical range is used in a sense that numerical values described before and after “to” are included as a lower limit value and an upper limit value.
Hereinafter, embodiments of the present disclosure are described.
The first curable polymer of the present disclosure is a copolymer containing one or more type(s) of structural units (UX) represented by the following formula and one or more type(s) of other structural units other than the structural units (UX).
The above formula is also referred to as formula (UX).
In the formula (UX), R1 and R2 each independently represent a hydrogen atom, a hydroxyl group or an organic group. The organic group preferably contains no polar atoms such as oxygen atoms. The benzene ring optionally has a substituent other than a substituent (SX) represented by the following formula. n is an integer of 0 or more.
Such other structural unit is preferably a monovinyl aromatic compound-derived structural unit (UY) from the viewpoint of an enhancement in glass transition temperature (Tg) of a cured product of the first curable polymer of the present disclosure.
The monovinyl aromatic compound is a compound containing a structure in which one polymerizable vinyl group is linked to an aromatic ring. The polymerizable vinyl group may be a substituent on the aromatic ring, or a vinyl group contained in a cyclopentadiene ring fused to the aromatic ring.
Examples include styrene and vinylnaphthalene; alkyl-substituted styrenes such as methylstyrene, ethylstyrene, and t-butylstyrene; alkyl-substituted vinylnaphthalenes; other alkyl-substituted aromatic vinyl compounds; dialkyl-substituted styrenes such as dimethylstyrene; other dialkyl-substituted aromatic vinyl compounds; α-alkyl-substituted styrenes such as α-methylstyrene; other α-alkyl-substituted aromatic vinyl compounds; β-alkyl-substituted styrenes such as β-methylstyrene; other β-alkyl-substituted aromatic vinyl compounds; indene, acenaphthylene; and their derivatives such as substituted bodies and modified bodies.
When the monovinyl aromatic compound has structural isomers, any of ortho-, meta-, and para-isomers may be used.
Examples of the structural units (UY) include structural units represented by the following formulas (UY-1) to (UY-5).
The first curable polymer of the present disclosure is a novel compound, can be used in any application, and is suitable for use in a curable composition, a prepreg, a multilayer body, a metal clad laminate and a wiring board, for example.
The present inventors have investigated and found that the dielectric dissipation factor (Df) under high-frequency conditions of a (semi-)cured product of a curable composition can be effectively reduced by using the first curable polymer of the present disclosure.
The content of the one or more type(s) of structural units (UX) based on a total amount of 100% by mol of all the structural units in the first curable polymer of the present disclosure is not particularly limited. The present inventors have investigated and found that the higher the content of the structural units (UX), the higher the dielectric dissipation factor (Df) under high-frequency conditions of the (semi-)cured product of the curable composition tends to be, in comparison when conditions other than the content of the structural units (UX) are uniform.
A copolymer containing one or more type(s) of structural units (UX) and one or more type(s) of other structural units other than the structural units (UX) (preferably, monovinyl aromatic compound-derived structural units (UY)) as structural units, rather than a homopolymer or copolymer containing only one or more type(s) of structural units (UX), tends to be able to effectively reduce the dielectric dissipation factor (Df) under high-frequency conditions of the (semi-) cured product of the curable composition.
The curable polymer of the present disclosure is preferably a copolymer containing one or more type(s) of structural units (UX) and one or more type(s) of monovinyl aromatic compound-derived structural units (UY) since the dielectric dissipation factor (Df) under high-frequency conditions of the (semi-)cured product of the curable composition can be effectively reduced.
The content of the one or more type(s) of structural units (UX) based on a total amount of 100% by mol of all the structural units in the first curable polymer of the present disclosure is preferably 1 to 90% by mol, more preferably 5 to 80% by mol, particularly preferably 5 to 70% by mol, and most preferably 10 to 50% by mol since the dielectric dissipation factor (Df) under high-frequency conditions of the (semi-)cured product of the curable composition can be effectively reduced.
The second curable polymer of the present disclosure is a homopolymer or copolymer containing only one or more type(s) of structural units (UX) represented by the following formula as structural units, and is for production of a prepreg, a metal clad laminate or a wiring board.
The above formula is also referred to as formula (UX), as in the first curable polymer of the present disclosure.
In the formula (UX), R1 and R2 each independently represent a hydrogen atom, a hydroxyl group or an organic group. The organic group preferably contains no polar atoms such as oxygen atoms. The benzene ring optionally has a substituent other than a substituent (SX) represented by the following formula. n is an integer of 0 or more.
The present inventors have investigated and found that the dielectric dissipation factor (Df) under high-frequency conditions of a (semi-)cured product of a curable composition can be effectively reduced by using the second curable polymer of the present disclosure.
In the structural units (UX) contained in the first and second curable polymers of the present disclosure, R1 and R2 preferably each independently represent an optionally substituted alkyl group or an optionally substituted phenyl group.
R1 and R2 preferably contain no polar atoms such as oxygen atoms since the dielectric dissipation factor (Df) under high-frequency conditions of the (semi-) cured product of the curable composition can be effectively reduced.
When R1 and/or R2 are/is alkyl group(s), the alkyl group(s) may be linear or branched, and are/is preferably linear.
When R1 and/or R2 are/is alkyl group(s), the number of carbon atoms in the alkyl group(s) is preferably 1 to 18, more preferably 1 to 12, and particularly preferably 1 to 8 from the viewpoint of the ease of synthesis of raw material monomers.
When R1 and/or R2 are/is optionally substituted phenyl group(s), the dielectric dissipation factor (Df) under high-frequency conditions of the (semi-) cured product of the curable composition tends to be able to be more effectively reduced. The reason for this is considered because, when R1 and/or R2 are/is optionally substituted phenyl group(s), molecular motion of a polymer obtained by (semi-)curing the curable polymer is effectively suppressed even under potential application.
Here, when R1 and/or R2 are/is optionally substituted phenyl group(s), a resin obtained in the case of single curing of the curable polymer may be hard and brittle, and impracticable for a prepreg, a metal clad laminate or a wiring board. In this case, other appropriate curable compound can be used in combination to improve brittleness of the resulting resin to a practical level for a prepreg, a metal clad laminate or a wiring board.
In the structural units (UX) contained in the first and second curable polymers of the present disclosure, the substituent (SX) may be attached to the benzene ring at any of ortho-, meta- and para-positions, and is preferably at para-position from the viewpoint of the ease of synthesis of raw material monomers, the ease of synthesis of the first and second curable polymers of the present disclosure, and the like.
The benzene ring in the structural unit (UX) may have a further substituent other than the substituent (SX). Examples of such a further substituent that may be contained in the benzene ring include an alkyl group having 1 to 18 carbon atoms and an aryl group. From the viewpoint of availability of raw materials, preferred are a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a phenyl group and a tolyl group. The benzene ring in the formula (UX) preferably has no substituent other than the substituent (SX).
In the structural units (UX), n is an integer of 0 or more, preferably 1 to 18, more preferably 1 to 12, particularly preferably 1 to 8, and most preferably 1 to 3.
The first and second curable polymer of the present disclosure may be either a thermosetting polymer or an active energy-ray curable polymer. The active energy-ray curable polymer is a polymer cured by irradiation with an active energy ray, such as an ultraviolet ray and an electron beam, and is preferably a thermosetting polymer for applications such as a metal clad laminate and a wiring board.
The first curable polymer of the present disclosure, including one or more type(s) of structural units (UX) and one or more type(s) of other structural units other than the structural units (UX), can be produced by copolymerization of one or more type(s) of monomers (MX) represented by the following formula and one or more type(s) of other monomers other than the monomers (MX) (preferably one or more type(s) of monovinyl aromatic compounds) copolymerizable therewith. In other words, the first curable polymer of the present disclosure is a copolymer of the one or more type(s) of monomers (MX) and one or more type(s) of other monomers other than the monomers (MX) (preferably one or more type(s) of other monomers containing one or more type(s) of monovinyl aromatic compounds) copolymerizable therewith.
The second curable polymer of the present disclosure, including only one or more type(s) of structural units (UX) as structural units, can be produced by homopolymerization or copolymerization of one or more type(s) of monomers (MX) represented by the following formula. In other words, the second curable polymer of the present disclosure is a homopolymer or copolymer of one or more type(s) of monomers (MX).
The above formula is also referred to as formula (MX).
In the formula (MX), R1 and R2 each independently represent a hydrogen atom, a hydroxyl group or an organic group. The organic group preferably contains no polar atoms such as oxygen atoms. The benzene ring optionally has a substituent other than the substituent in the above formula. n is an integer of 0 or more. Preferred R1, preferred R2, and preferred n are the same as defined for the formula (UX).
The polymerization method is preferably chain polymerization or the like. Examples of the chain polymerization include cationic polymerization, anionic polymerization and radical polymerization, and cationic polymerization or the like is preferred.
The monomer (MX) can be synthesized by a known method with chloroalkylstyrene such as chloromethylstyrene (CMS), as a starting material. The monomer (MX) is preferably a CMS-modified body obtained with chloromethylstyrene (CMS) as a starting material.
Hereinafter, there is shown an example of the reaction scheme of synthesis of the monomer (MX) with chloromethylstyrene (CMS) as a starting material and the reaction scheme of polymerization using the resulting monomer (MX). In this example, in the monomer (MX), the substituent (SX) is attached to the benzene ring at para-position, and n is 1. This example shows copolymerization of the resulting monomer and styrene as the monovinyl aromatic compound.
Examples of the first curable polymer of the present disclosure include copolymers represented by the following formulas (MC-11) to (MC-20). The arrangement of the structural units in such a copolymer may be any of alternate, block, and random arrangements.
In the formulas (MC-11) to (MC-20), m and n represent the numbers of moles of the respective structural units, and m>0 and n>0 are satisfied. In these formulas, n is independent of n in the formulas (MX) and (SX).
When the total number of moles of m and n is 100% by mol, the mole fraction of m is preferably 1 to 90% by mol, and more preferably 5 to 80% by mol, and the mole fraction of n is preferably 99 to 10% by mol, and more preferably 95 to 20% by mol.
In the copolymers represented by the formulas (MC-11) to (MC-20), the number n of carbon atoms in an alkylene group as a binding group of Si and the benzene ring is 1. Examples of the first curable polymer of the present disclosure also include copolymers in which the number n of carbon atoms in an alkylene group as a binding group of Si and the benzene ring in the copolymers represented by the formulas (MC-11) to (MC-20) is modified to an integer of 0 or more except for 1 (e.g., 0, 2 and 3). Specific examples of such copolymers in which the number n of carbon atoms in an alkylene group as a binding group of Si and the benzene ring is an integer of 0 or more except for 1 include copolymers (P24) and (P25) in the Examples section below.
Examples of the second curable polymer of the present disclosure include homopolymers represented by the following formulas (MC-21) and (MC-22).
In the formulas (MC-21) and (MC-22), m represents the number of moles of the structural unit, and m>0 is satisfied. m is preferably 5 to 250, and more preferably 10 to 200.
In the copolymers represented by the formulas (MC-21) and (MC-22), the number n of carbon atoms in an alkylene group as a binding group of Si and the benzene ring is 1. Examples of the second curable polymer of the present disclosure also include homopolymers in which the number n of carbon atoms in an alkylene group as a binding group of Si and the benzene ring in the copolymers represented by the formulas (MC-21) and (MC-22) is modified to an integer of 0 or more except for 1 (e.g., 0, 2 and 3).
Other examples of the second curable polymer of the present disclosure include a copolymer having a combined structure of the formula (MC-21) and the formula (MC-22). Also in this copolymer, the number n of carbon atoms in an alkylene group as a binding group of Si and the benzene ring can be modified to an integer of 0 or more except for 1 (e.g., 0, 2 and 3).
The molecular weight of each of the first and second curable polymers of the present disclosure is not particularly limited. The number average molecular weight (Mn) is preferably 1000 to 30000, and more preferably 5000 to 17000. The weight average molecular weight (Mw) is preferably 5000 to 100000, and more preferably 10000 to 90000.
The first and second curable polymers of the present disclosure can each have a structure containing no polar atoms in a main chain, unlike a modified polyphenylene ether (modified PPE) oligomer having a polymerizable functional group at each of both ends, or the like.
The first and second curable polymers of the present disclosure can each have a structure containing no polar atoms or few polar atoms. The first and second curable polymers of the present disclosure each preferably have a structure containing no polar atoms.
A resin with effectively reduced dielectric dissipation factor (Df) under high-frequency conditions can be obtained by using the first curable polymer of the present disclosure or the second curable polymer of the present disclosure, the polymer containing no polar atoms or few polar atoms.
Hereinafter, the first curable polymer of the present disclosure and the second curable polymer of the present disclosure are collectively simply referred to as “the curable polymer of the present disclosure”.
The curable composition of the present disclosure includes one or more type(s) of the curable polymers of the present disclosure.
The curable composition of the present disclosure can include, if necessary, one or more type(s) of other curable compounds having one or more type(s) of polymerizable functional groups.
When the curable polymer of the present disclosure is singly cured and formed into a resin, such a resin, while depends on the molecular structure of the curable polymer, may be hard and brittle, and impracticable for a prepreg, a metal clad laminate or a wiring board. In this case, other appropriate curable compound can be used in combination to improve brittleness of the resulting resin to a practical level for a prepreg, a metal clad laminate or a wiring board.
The curable polymer of the present disclosure and other appropriate curable compound may be used in combination to enable the glass transition temperature (Tg) of the (semi-)cured product of the curable composition to be enhanced.
The curable composition of the present disclosure can further include, if necessary, one or more type(s) of optional components.
The curable composition of the present disclosure may be either a thermosetting composition or an active energy-ray curable composition, and is preferably a thermosetting composition for applications such as a metal clad laminate and a wiring board.
Such other curable compound may be a monofunctional compound having one type of polymerizable functional groups, or may be a polyfunctional compound having two or more polymerizable functional groups.
Examples of the polymerizable functional group include a polymerizable carbon-carbon unsaturated bond-containing group, an epoxy group, an isocyanate group, a hydroxy group, a mercapto group, an amino group, a ureido group, a carboxy group, a sulfonic acid group, an acid chloride group, and a chlorine atom. Examples of the polymerizable carbon-carbon unsaturated bond-containing group include a vinyl group, an allyl group, a dienyl group, a (meth)acryloyloxy group, and a (meth)acrylamino group.
Examples of such other curable compound include curable compounds which, when singly cured, are formed into resins such as a polyphenylene ether resin (PPE), a bismaleimide resin, an epoxy resin, a fluorine resin, a polyimide resin, an olefin resin, a polyester resin, a polystyrene resin, a hydrocarbon elastomer, a benzoxazine resin, an active ester resin, a cyanate ester resin, a butadiene resin, a hydrogenated or non-hydrogenated styrene-butadiene resin, a vinyl resin, a cycloolefin polymer, an aromatic polymer, and a divinyl aromatic polymer.
Examples of forms of such other curable compound include a monomer, an oligomer and a prepolymer.
Such other curable compound is represented by, for example, the following formula (PPE-o), and examples include a modified polyphenylene ether (modified PPE) oligomer having a polymerizable functional group at each of both ends.
m and n in the formula (PPE-o) are independent of m and n in the formulas (MX), (SX), (MC-11) to (MC-22).
X at both ends of the formula (PPE-o) each independently represents a group represented by the following formula (x1) or formula (x2), where “*” represents a bond to an oxygen atom.
In the formula (PPE-o), m is preferably 1 to 20, more preferably 3 to 15, and n is preferably 1 to 20, more preferably 3 to 15.
The number average molecular weight (Mn) of the modified polyphenylene ether (modified PPE) oligomer is not particularly limited, and is preferably 1000 to 5000, and more preferably 1000 to 4000.
Also in a case where the curable polymer of the present disclosure and other curable compound containing polar atoms in a main chain, for example, the modified polyphenylene ether (modified PPE) oligomer, are used in combination in the curable compound, the amount of polar atoms contained in the (semi-)cured product of the curable composition can be reduced as compared with a case where only a curable compound containing many polar atoms, such as a modified PPE oligomer, is used in the curable compound. As a result, the dielectric dissipation factor (Df) of the (semi-)cured product of the curable composition can be effectively reduced.
The content of one or more type(s) of the curable polymers of the present disclosure based on a total amount of 100 parts by mass of one or more type(s) of the curable polymers of the present disclosure and one or more type(s) of other curable compounds, in the curable composition of the present disclosure is preferably 20 to 100 parts by mass, more preferably 30 to 100 parts by mass, particularly preferably 50 to 100 parts by mass, and most preferably 70 to 100 parts by mass since the dielectric dissipation factor (Df) under high-frequency conditions of the (semi-)cured product of the curable composition can be effectively reduced.
The curable composition preferably includes one or more type(s) of polymerization initiators. As the polymerization initiators, organic peroxides, azo-based compounds, other known polymerization initiators and combinations thereof can be used. Specific examples thereof include dicumyl peroxide, benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydro peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, di-t-butyl peroxide, t-butylcumyl peroxide, α,α′-di(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di-t-butyl peroxyisophthalate, t-butyl peroxybenzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di(trimethylsilyl)peroxide, trimethylsilyl triphenylsilyl peroxide and azobisisobutyronitrile.
The curable composition can optionally contain one or more type(s) of additives, such as an inorganic filler (also referred to as a filler), a compatibilizers and a flame retardant, if necessary.
Examples of the inorganic filler include metal oxides such as silica (e.g. spherical silica), alumina, titanium oxide and mica; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; talc; aluminum borate; barium sulfate; and calcium carbonate. One or more type(s) of these can be used. Among them, silica, mica, talc and the like are preferred, and spherical silica is more preferred, from the viewpoint of low thermal expansion.
The inorganic filler may be surface-treated with a silane coupling agent of an epoxy silane type, a vinyl silane type, a methacrylic silane type or an amino silane type. The timing of the surface treatment with the silane coupling agent is not particularly limited. The inorganic filler surface-treated with the silane coupling agent may be prepared in advance, or the silane coupling agent may be added by an integral blend method during the preparation of the curable composition.
Examples of the flame retardant include a halogen flame retardant and a phosphorus flame retardant. One or more type(s) of these can be used. Examples of the halogen flame retardant include brominated flame retardants such as pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A and hexabromocyclododecane; and chlorinated flame retardants such as chlorinated paraffin. Examples of the phosphorus flame retardant include phosphates such as a fused phosphate and a cyclic phosphate; phosphazene compounds such as a cyclic phosphazene compound; phosphinate flame retardants such as an aluminum dialkylphosphinate salt; melamine flame retardants such as melamine phosphate and melamine polyphosphate; and phosphine oxide compounds having a diphenylphosphine oxide group.
The curable composition may optionally contain one or more type(s) of organic solvents, if necessary. Examples of the organic solvents include, but are not particularly limited to, ketones such as methyl ethyl ketone; ethers such as dibutyl ether; esters such as ethyl acetate; amides such as dimethylformamide; aromatic hydrocarbons such as benzene, toluene and xylene; and chlorinated hydrocarbons such as trichloroethylene.
In the curable composition, the formulation composition and solid concentration can be appropriately designed.
The formulation composition of the curable composition can be designed so that the resulting (semi-)cured product is not embrittled and properties of the resulting (semi-)cured product, for example, the dielectric dissipation factor (Df) and the glass transition temperature (Tg) are suitable.
In applications such as a prepreg, the solid concentration of the curable composition can be designed so that the fibrous substrate is easily impregnated with the curable composition, and is preferably 50 to 90% by mass.
The prepreg of the present disclosure include a fibrous substrate and a (semi-)cured product of the curable composition of the present disclosure.
The prepreg can be produced by impregnating a fibrous substrate with the curable composition and (semi-)curing, for example, by thermal curing.
The (semi-)cured product can include a singly cured product of one of the curable polymer of the present disclosure, a reaction product of a plurality of the curable polymers of the present disclosure, or a reaction product of one or more type(s) of the curable polymers of the present disclosure and one or more type(s) of other curable compounds.
The (semi-)cured product can include, if necessary, an additive such as an inorganic filler (filler).
Examples of the material of the fibrous substrate include, but are not particularly limited to, inorganic fibers such as a glass fiber, a silica fiber and a carbon fiber; organic fibers such as an aramid fiber and a polyester fiber; and combinations thereof. In applications such as a metal clad laminate and a wiring board, the glass fiber or the like is preferred. Examples of forms of the glass fibrous substrate include glass cloth, glass paper and glass mat.
Curing conditions for the curable composition can be set according to the composition of the curable composition, and semi-curing conditions (conditions under which complete curing does not occur) are preferred.
Thermal curing by heating at, for example, 80 to 180° C. for 1 to 10 minutes is preferred.
In applications such as a metal clad laminate and a wiring board, it is preferable to adjust the composition of the curable composition and curing conditions so that the resin content in the resulting prepreg is in the range of 40 to 80% by mass.
The first multilayer body of the present disclosure includes a substrate and a curable composition layer consisting of the curable composition of the present disclosure described above.
The second multilayer body of the present disclosure includes a substrate and a (semi-)cured product-containing layer containing the (semi-)cured product of the curable composition of the present disclosure described above.
In the first and second multilayer bodies of the present disclosure, examples of the substrate include, but are not particularly limited to, a resin film, a metal foil and a combination thereof.
The (semi-)cured product-containing layer may be a layer containing a fibrous substrate and a (semi-)cured product of the curable composition of the present disclosure.
The resin film is not particularly limited, and a known resin film is available. Examples of constituent resins of the resin film include polyimide, polyethylene terephthalate (PET), polyethylene naphthalate, cycloolefin polymer and polyether sulfide.
Due to its low electrical resistance, the metal foil is preferably copper foil, silver foil, gold foil, aluminum foil and combinations thereof, and more preferably copper foil and the like.
The metal clad laminate of the present disclosure includes an insulating layer containing a cured product of the curable composition of the present disclosure and metal foil.
The insulating layer may be a layer containing a fibrous substrate and a cured product of the curable composition of the present disclosure.
Due to its low electrical resistance, the metal foil is preferably copper foil, silver foil, gold foil, aluminum foil and combinations thereof, and more preferably copper foil and the like. The metal foil may have a metal plating layer on its surface. The metal foil may be a metal foil with a carrier including an ultra-thin metal foil and a carrier metal foil supporting the ultrathin metal foil. The metal foil may have at least one surface subjected to surface treatments such as anticorrosion, silanization, roughening and barrier-forming treatment.
The thickness of the metal foil is not particularly limited but is preferably 0.1 to 100 μm, more preferably 0.2 to 50 μm, and particularly preferably 1.0 to 40 μm since it is suitable for the formation of a conductive pattern (also referred to as a circuit pattern) such as wiring.
The metal clad laminate may be a single-sided metal clad laminate with metal foil on one side or a double-sided metal clad laminate with metal foil on both sides and is preferably a double-sided metal clad laminate.
The single-sided metal clad laminate can be produced by stacking one or more of the above prepregs and metal foil and heating and pressing the resulting first temporary multilayer body.
The double-sided metal clad laminate can be produced by sandwiching one or more of the above prepregs between a pair of metal foils and heating and pressing the resulting first temporary multilayer body.
A metal clad laminate that uses copper foil as the metal foil is referred to as a copper clad laminate (CCL).
The insulating layer preferably consists of a heat-pressed product of the prepreg, which contains a fibrous substrate and a resin and may optionally contain one or more type(s) of additives such as an inorganic fillers and a flame retardant, if necessary. The heat-pressed product of the prepreg is also referred to as a composite substrate.
The heating and pressing conditions of the first temporary multilayer body are not particularly limited, and for example, a temperature of 170 to 250° C., a pressure of 0.3 MPa to 30 MPa, and a time of 3 to 240 minutes are preferred.
The metal clad laminate 1 shown in
The metal clad laminate 2 shown in
The metal clad laminates 1 and 2 may have layers other than those described above.
The metal clad laminates 1 and 2 can have an adhesive layer between the composite substrate (cured product-containing layer) 11 and the metal foil (metal layer) 12 in order to enhance the adhesion therebetween. As the material of the adhesive layer, a known material is available. Examples thereof include an epoxy resin, a cyanate ester resin, an acrylic resin, a polyimide resin, a maleimide resin, an adhesive fluororesin and combinations thereof. Examples of commercially available adhesive fluororesins include “Fluon LM-ETFE LH-8000,” “AH-5000,” “AH-2000” and “EA-2000,” all of which are manufactured by AGC Inc.
The thickness of the composite substrate can be designed as appropriate according to the application. From the viewpoint of preventing disconnection of the wiring board, the thickness is preferably 50 μm or more, more preferably 70 μm or more, and particularly preferably 100 μm or more. From the viewpoint of flexibility, miniaturization, and weight reduction of the wiring board, the thickness is preferably 300 μm or less, more preferably 250 μm or less, and particularly preferably 200 μm or less.
The wiring board of the present disclosure includes an insulating layer containing a cured product of the curable composition of the present disclosure and wiring.
The wiring board can be manufactured by forming a conductive pattern (circuit pattern) such as wiring using the metal foil on the outermost surface of the metal clad laminate of the present disclosure described above. Examples of methods of forming a conductive pattern such as wiring include a subtractive method, in which metal foil is etched to form wiring or the like, and modified semi additive process (MSAP), in which metal foil is plated to form wiring on the metal foil.
The wiring board 3 is composed of a heat-pressed product of the prepreg, in which the conductive pattern (circuit pattern) 22 such as wiring 22W is formed on at least one surface of the composite substrate (cured product-containing layer, insulating layer) 11 containing a cured product of the curable composition of the present disclosure.
One or more prepreg(s) may be further stacked on the resulting wiring board, which is sandwiched between a pair of metal foils, and the obtained second temporary multilayer body may be heated and pressed to form a conductive pattern of wiring or the like using the outermost metal foil, thereby manufacturing a multilayer wiring board (also referred to as a multilayer printed wiring board). The outermost metal foil may be arranged only on one side of the second temporary multilayer body.
The wiring board of the present disclosure is suitable for use in a high-frequency region (a region with a frequency of 1 GHz or higher).
In recent applications such as portable electronic devices, signals have become increasingly high-frequency as higher speeds and larger capacities of communication have been achieved. The wiring board used in the such applications is required to have reduced transmission loss in the high-frequency region. For this reason, the resin contained in the composite substrate for the wiring board used in the above applications is required to have reduced dielectric loss in the high-frequency region. The dielectric dissipation factor (Df) generally depends on frequency. Given the same material, the higher the frequency, the larger the dielectric dissipation factor (Df) tends to be. The resin contained in the composite substrate preferably has a low dielectric dissipation factor (Df) under high-frequency condition.
The wiring board may be used in a relatively high-temperature environment. Even in this case, in order to ensure the reliability of the wiring board, the resin contained in the prepreg and the composite substrate preferably has a sufficiently high glass transition temperature (Tg).
If there is a big difference in coefficient of thermal expansion (CTE) between the prepreg or composite substrate and the metal foil, misalignment or delamination of the metal foil may occur when heating and pressing the first temporary multilayer body containing the prepreg and the metal foil or the second temporary multilayer body containing the composite substrate, the prepreg and the metal foil. Preferably, the difference in the coefficient of thermal expansion (CTE) between the prepreg or composite substrate and the metal foil is small. Since the resin generally has a larger coefficient of thermal expansion (CTE) than the metal foil, a lower coefficient of thermal expansion (CTE) for the prepreg and composite substrate is preferred.
The present inventors have investigated and found that the dielectric dissipation factor (Df) under high-frequency conditions of the (semi-)cured product of the curable composition can be effectively reduced by using the curable polymer of the present disclosure, the polymer containing no polar atoms or few polar atoms.
It was also found that the (semi-)cured product of the curable composition containing the curable polymer of the present disclosure had a sufficiently high glass transition temperature (Tg).
It was also found that the (semi-)cured product of the curable composition containing the curable polymer of the present disclosure had a sufficiently low coefficient of thermal expansion (CTE).
In addition, it was found that the (semi-)cured product of the curable composition containing the curable polymer of the present disclosure also had a practically good adhesion to metals such as copper foil.
By using the curable polymer of the present disclosure, it is possible to obtain a resin with effectively reduced dielectric dissipation factor (Df) under high-frequency conditions and sufficiently high glass transition temperature (Tg). This (semi-)cured product is suitable for a composite substrate, an insulating layers and the like, which are suitable for wiring boards used in the high-frequency region.
The dielectric dissipation factor (Df) of the (semi-)cured product of the curable composition of the present disclosure and the composite substrate containing the same under high-frequency conditions is preferably within, for example, the following ranges.
The dielectric dissipation factor (Df) at a frequency of 10 GHz is preferably smaller, preferably 0.010 or less, more preferably 0.005 or less, further preferably 0.003 or less, particularly preferably 0.002 or less, and most preferably less than 0.002.
The dielectric dissipation factor (Df) at a frequency of 10 GHz can be 0.0018 or less, 0.0016 or less, 0.0014 or less, 0.0012 or less, or 0.0010 or less.
The lower limit of the dielectric dissipation factor (Df) at a frequency of 10 GHz is not particularly limited, and is, for example, 0.0001.
The glass transition temperature (Tg) of the (semi-)cured product of the curable composition of the present disclosure is preferably 130° C. or higher, more preferably 150° C. or higher, and particularly preferably 180° C. or higher. The upper limit is not particularly limited, for example, 300° C.
The coefficient of thermal expansion (CTE) of the (semi-)cured product of the curable composition of the present disclosure and the composite substrate containing the same is preferably within, for example, the following ranges.
The coefficient of thermal expansion (CTE) is preferably smaller, preferably 70 ppm/° C. or less, and more preferably 60 ppm/° C. or less. The lower limit thereof is not particularly limited, for example, 1 ppm/° C.
The dielectric dissipation factor (Df) and glass transition temperature (Tg) can be measured by methods described in the Examples section below.
The coefficient of thermal expansion (CTE) can be measured with a commercially available thermomechanical analyzer, by a known method.
As described above, the present disclosure can provide a curable polymer capable of producing a resin with effectively reduced dielectric dissipation factor (Df) under high-frequency conditions and sufficiently high glass transition temperature (Tg), and a curable composition containing the same.
Although the curable polymer of the present disclosure and the curable composition including the same are suitable for applications such as a prepreg, a metal clad laminate and a wiring board, they can be used in any application.
The curable polymer of the present disclosure and the curable composition including the same are suitable for applications such as a prepreg, a metal clad laminate and a wiring board.
The metal clad laminate of the present disclosure is suitable for use as a wiring board, for example, for various electrical and electronic devices.
The wiring board of the present disclosure is suitable for use, for example, in portable electronic devices such as a mobile phone, a smartphone, a personal digital assistant and a laptop computer; antennas for a mobile phone base station and a vehicle; electronic devices such as a server, a router and a backplane; wireless infrastructures; radars for collision avoidance and the like; and various sensors (e.g., automotive sensors such as engine management sensors).
The wiring board of the present disclosure is particularly suitable for applications in which communication is performed using a high-frequency signal and various applications in which a reduction in transmission loss is required in a high-frequency region.
Hereinafter, the present disclosure is described in detail with reference to examples, but the present disclosure is not limited thereto. Examples 11, 12, 21 to 25, 31, 41, 51, 61, 71, 81, 91, 101 to 115, 121, and 301 are Examples, while Example 201 is Comparative Example. Unless otherwise specified, room temperature is around 25° C.
In the Examples section, commercially available catalysts and reagents were used as received for reactions unless otherwise specified. The solvents used were dehydrated and deoxygenated commercial solvents.
The structure of the synthesized monomer was identified using a nuclear magnetic resonance device (“AVANCE NEO400” manufactured by Bruker) by carrying out 1H-NMR measurement.
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the synthesized curable polymer were determined by a gel permeation chromatography (GPC) method. The GPC device used was “HLC-8320GPC” manufactured by Tosoh Corporation, provided with a differential refractive index detector (RI detector). The eluent used was tetrahydrofuran. The column used was one in which four columns of “TSKgel SuperHZ2000”, “TSKgel SuperHZ2500”, “TSKgel SuperHZ3000” and “TSKgel SuperHZ4000” (all were manufactured by Tosoh Corporation) were connected in series. A sample solution was prepared by dissolving 20 mg of a resin in 2 mL of tetrahydrofuran. Injected was 10 μl of the sample solution, and chromatogram was measured. GPC measurement was carried out by using 10 standard polystyrenes having a molecular weight within a range of 400 to 5000000, and the calibration curve representing the relationship between the retention time and the molecular weight was created. The Mn and Mw of the curable polymer were determined based on the calibration curve.
(Dielectric Constant (Dk) and Dielectric Dissipation Factor (Df))
Dielectric constant (Dk) and dielectric dissipation factor (Df) at 10 GHz of the evaluation sample (cured film product) were measured by the SPDR method using a vector network analyzer (“E8361C” manufactured by Agilent Technologies) at room temperature.
Dynamic mechanical analysis (DMA) was taken on the evaluation sample (cured film product) using a dynamic viscoelasticity measuring device (“DVA 200” manufactured by IT Keisoku Seigyo Co., Ltd.) to measure the glass transition temperature (Tg) (° C.) under conditions of a frequency of 10 Hz, a heating rate of 2° C./min, and a temperature range of 25° C. to 300° C.
Under a nitrogen atmosphere, a 1 L four-necked flask was charged with magnesium (turning, 7.96 g, 328 mmol) and diethyl ether (327 mL), and the mixture was cooled in an ice bath. Iodine (250 mg, 0.985 mmol) was added to this suspension, 4-(chloromethyl) styrene (50.0 g, 328 mmol) was then added dropwise over one hour, and the mixture was further stirred for one hour. Chlorodimethylvinylsilane (51.9 mL, 377 mmol) was added dropwise to the reaction mixture over 30 minutes, the flask was then warmed to room temperature and the mixture was then stirred for 20 hours. The flask was cooled to 0° C., a saturated aqueous ammonium chloride solution (328 mL) was added for quenching, and an insoluble matter was then removed by filtration. The filtrate was left to still stand, followed by extraction to separate an organic phase. Ethyl acetate (328 mL) was further added to the water phase, followed by extraction to separate the organic phase. The organic phases obtained from these extractions were combined, the combined organic phases were dried over magnesium sulfate and filtered, and the filtrate was concentrated under vacuum to give a crude product. The crude product was purified by silica gel column chromatography (mobile phase: n-hexane) to give 59.0 g of dimethylvinylsilane A (dimethyl(vinyl)(4-vinylbenzyl)silane) as a colorless liquid (yield: 86%). The resulting compound was one monomer (MX) (R1=methyl group, R2=methyl group, n=1).
The reaction scheme and results of NMR analysis are as follows:
1H-NMR (CDCl3): δ (ppm) 7.26 (d, 2H, J=8.34 Hz, Ar-H), 6.96 (d, 2H, J=8.34 Hz, Ar-H), 6.67 (dd, 1H, J=10.85, 17.52 Hz), 6.12 (dd, J=14.66, 20.03 Hz, 1H), 5.96 (dd, 1H, J=3.93, 14.66 Hz), 5.69-5.63 (m, 2H), 5.14 (dd, 1H, J=0.83, 10.85 Hz), 2.13 (s, 2H), 0.05 (s, 6H).
Under a nitrogen atmosphere, a 500 mL four-necked flask was charged with magnesium (turning, 1.50 g, 61.7 mmol) and tetrahydrofuran (65 mL), and the mixture was cooled in an ice bath. Iodine (53.9 mg, 0.212 mmol) was added to this suspension, 4-bromostyrene (9.67 g, 52.8 mmol) was then added dropwise, and the mixture was stirred at room temperature for 15 minutes and stirred under a heating condition at 70° C. for one hour. The reaction mixture was cooled to room temperature, magnesium (turning, 0.40 g, 16.3 mmol) was added, and the mixture was heated under reflux for one hour. The reaction mixture was again cooled to room temperature, chlorodimethylvinylsilane (8.04 g, 66.6 mmol) was added dropwise, and the mixture was then stirred at room temperature for one hour. The flask was cooled to 0° C., a saturated aqueous ammonium chloride solution (100 mL) was added and the mixture was stirred and quenched at room temperature overnight, and ethyl acetate was then added, followed by extraction to separate the organic phase. The organic phase obtained from such extraction was dried over magnesium sulfate and filtered, and the filtrate was concentrated under vacuum to give a crude product. The crude product was purified by silica gel column chromatography (mobile phase: n-hexane) to give 6.58 g of dimethylvinylsilane B (dimethyl(vinyl)(4-vinylphenyl)silane) as a colorless liquid (yield: 54%). The resulting compound was one monomer (MX) (R1=methyl group, R2=methyl group, n=0).
The reaction scheme and results of NMR analysis are as follows:
1H-NMR (CDCl3): δ (ppm) 7.57-7.45 (m, 2H), 7.46-7.36 (m, 2H), 6.71 (dd, 1H, J=10.9, 17.6 Hz), 6.28 (dd, 1H, J=14.6, 20.2 Hz), 6.05 (dd, 1H, J=3.8, 14.6 Hz), 5.82-5.70 (m, 2H), 5.26 (dd, 1H, J=1.0, 10.9 Hz), 0.34 (s, 6H).
Under a nitrogen atmosphere, a 500 mL four-necked flask was charged with a hexane solution of n-butyllithium (28.8 mL, 46 mmol) and diisopropylamine (6.5 mL, 46 mmol), and the mixture was stirred at −78° C. This solution was charged with a solution of 4-methylstyrene (5.0 g, 42 mmol) in tetrahydrofuran (40 mL), and the mixture was again stirred at −78° C. This solution was warmed to room temperature, (chloromethyl)dimethylvinylsilane (7.5 mL, 50 mmol) was then added, and the mixture was stirred at 50° C. for 12 hours. The flask was cooled to room temperature, an aqueous ammonium chloride solution was added for quenching, and a crude liquid was then concentrated under vacuum. This concentrated product was purified by silica gel column chromatography (mobile phase: n-hexane) and gel permeation chromatography (GPC) to give 3.2 g of dimethylvinylsilane C (dimethyl(vinyl)(2-(4-vinylphenyl)ethyl)silane) (yield: 35%). The resulting compound was one monomer (MX) (R1=methyl group, R2=methyl group, n=2).
The reaction scheme and results of NMR analysis are as follows:
1H-NMR (CDCl3): δ (ppm) 7.33 (d, 2H, J=8.0 Hz), 7.20-7.08 (m, 2H), 6.70 (dd, 1H, J=17.6, 10.9 Hz), 6.16 (dd, 1H, J=20.2, 14.7 Hz,), 5.99 (dd, 1H, J=14.7, 3.9 Hz), 5.80-5.60 (m, 2H), 5.19 (dd, 1H, J=10.9, 1.0 Hz), 2.72-2.42 (m, 2H), 1.03-0.79 (m, 2H), 0.10 (s, 6H).
Under a nitrogen atmosphere, a 500 mL four-necked flask was charged with magnesium (turning, 1.59 g, 65.4 mmol) and diethyl ether (65.4 mL), and the mixture was cooled in an ice bath. A small amount of iodine was added to this suspension, a solution of 4-(chloromethyl) styrene (10.0 g, 65.5 mmol) in diethyl ether (65.4 mL) was then added dropwise over 1.5 hours, and the mixture was further stirred for one hours. Chloro(methyl)(phenyl)(vinyl)silane (13.9 mL, 78.4 mmol) was added dropwise to the reaction mixture over 10 minutes, the flask was then warmed to room temperature, and the mixture was stirred for 22 hours. The flask was cooled to 0° C., and a saturated aqueous ammonium chloride solution (131 mL) was added for quenching, followed by extraction to separate an organic phase. Diethyl ether (100 mL) was further added to the water phase, and extraction was performed twice to separate the organic phase. The organic phases obtained from these extractions were combined, the combined organic phases were dried over magnesium sulfate and filtered, and the filtrate was concentrated under vacuum to give a crude product. The crude product was purified by silica gel column chromatography (mobile phase: n-hexane) to give 15.0 g of methyl(phenyl)(vinyl)(4-vinylbenzyl)silane as a colorless liquid (yield: 86%). The resulting compound was one monomer (MX) (R1=methyl group, R2=phenyl group, n=1).
The reaction scheme and results of NMR analysis are as follows:
1H-NMR (CDCl3): δ (ppm) 7.46 (dm, 2H, J=7.75 Hz, Ar-H), 7.39-7.32 (m, 3H, Ar-H), 7.22 (d, 2H, J=7.99 Hz, Ar-H), 6.90 (d, 2H, J=7.87 Hz, Ar-H), 6.65 (dd, 1H, J=10.85, 17.52 Hz), 6.27 (ddd, 1H, J=1.19, 14.66, 20.15 Hz), 6.09 (ddd, 1H, J=1.19, 3.82, 14.78 Hz), 5.72 (ddd, 1H, J=1.19, 3.70, 20.15 Hz), 5.66 (dd, 1H, J=0.95, 17.64 Hz), 5.14 (d, 1H, J=10.85 Hz), 2.42 (d, 1H, J=13.71 Hz), 2.37 (d, 1H, J=13.71 Hz), 0.30 (d, 3H, J=1.19 Hz).
Under a nitrogen atmosphere, a 100 mL pressure-resistant reaction vessel was loaded with dimethylvinylsilane A (dimethyl(vinyl)(4-vinylbenzyl)silane) (6.7 g, 32.9 mmol) obtained in Synthesis Example 1, styrene (13.3 g, 128.2 mmol), toluene (20 g, 21.7 mmol), and a boron trifluoride-diethyl ether complex (0.36 g, 2.6 mmol), and the mixture was then reacted at 50° C. for five hours. After completion of the reaction, a saturated aqueous sodium hydrogen carbonate solution was loaded to the polymerization solution to stop the reaction. This polymerization solution was added dropwise into a large amount of methanol to precipitate a polymerized product. The precipitated product was recovered, washed and dried to give 12.0 g of copolymer (P11) (yield: 59.8%).
The same manner as in Example 11 was performed except that the amount of dimethylvinylsilane A (dimethyl(vinyl)(4-vinylbenzyl)silane) was modified to 9.0 g, 44.5 mmol, and the amount of styrene was modified to 11.0 g, 105.8 mmol, to give 11.9 g of copolymer (P12) (yield: 59.4%).
The reaction scheme of Examples 11 and 12 is as follows:
Under a nitrogen atmosphere, a 100 mL pressure-resistant reaction vessel was loaded with dimethylvinylsilane A (dimethyl(vinyl)(4-vinylbenzyl)silane) (4.6 g, 22.7 mmol), 4-methylstyrene (15.4 g, 130.4 mmol), toluene (20 g, 21.7 mmol), and a boron trifluoride-diethyl ether complex (0.36 g, 2.6 mmol), and the mixture was then reacted at 50° C. for five hours. After completion of the reaction, a saturated aqueous sodium hydrogen carbonate solution was loaded to the polymerization solution to stop the reaction. This polymerization solution was added dropwise into a large amount of methanol to precipitate a polymerized product. The precipitated product was recovered, washed and dried to give 19.4 g of copolymer (P21) (yield: 97.2%).
The same manner as in Example 21 was performed except that the amount of dimethylvinylsilane A (dimethyl(vinyl)(4-vinylbenzyl)silane) was modified to 6.0 g, 29.6 mmol, and the amount of 4-methylstyrene was modified to 14.0 g, 118.5 mmol, to give 19.3 g of copolymer (P22) (yield: 96.3%).
The same manner as in Example 21 was performed except that the amount of dimethylvinylsilane A (dimethyl(vinyl)(4-vinylbenzyl)silane) was modified to 8.4 g, 41.5 mmol, and the amount of 4-methylstyrene was modified to 11.6 g, 98.2 mmol, to give 18.9 g of copolymer (P23) (yield: 94.6%).
The reaction scheme of Examples 21 to 23 is as follows:
The same manner as in Example 21 was performed except that dimethylvinylsilane A (dimethyl(vinyl)(4-vinylbenzyl)silane) was changed to dimethylvinylsilane B (dimethyl(vinyl)(4-vinylphenyl)silane) (6.8 g, 29.8 mmol) obtained in Synthesis Example 2, and the amount of 4-methylstyrene was modified to 14.0 g, 118.8 mmol, to give 17.6 g of copolymer (P24) (yield: 84.7%).
The reaction scheme of Example 24 is as follows:
The same manner as in Example 21 was performed except that dimethylvinylsilane A (dimethyl(vinyl)(4-vinylbenzyl)silane) was changed to dimethylvinylsilane C (dimethyl(vinyl)(2-(4-vinylphenyl)ethyl)silane) (6.4 g, 29.7 mmol) obtained in Synthesis Example 3, and the amount of 4-methylstyrene was modified to 14.0 g, 118.4 mmol, to give 18.5 g of copolymer (P25) (yield: 91.0%).
The reaction scheme of Example 25 is as follows:
Under a nitrogen atmosphere, a 100 mL pressure-resistant reaction vessel was loaded with dimethylvinylsilane A (dimethyl(vinyl)(4-vinylbenzyl)silane) (4.8 g, 23.7 mmol) obtained in Synthesis Example 1, 4-tert-butylstyrene (15.2 g, 94.8 mmol), toluene (20 g, 21.7 mmol), and a boron trifluoride-diethyl ether complex (0.36 g, 2.6 mmol), and the mixture was then reacted at 50° C. for five hours. After completion of the reaction, a saturated aqueous sodium hydrogen carbonate solution was loaded to the polymerization solution to stop the reaction. This polymerization solution was added dropwise into a large amount of methanol to precipitate a polymerized product. The precipitated product was recovered, washed and dried to give 19.0 g of copolymer (P31) (yield: 95%).
The reaction scheme is as follows:
Under a nitrogen atmosphere, a 100 mL pressure-resistant reaction vessel was loaded with dimethylvinylsilane A (dimethyl(vinyl)(4-vinylbenzyl)silane) (6.0 g, 29.6 mmol) obtained in Synthesis Example 1, indene (14.0 g, 120.5 mmol), toluene (20 g, 21.7 mmol), and a boron trifluoride-diethyl ether complex (0.36 g, 2.6 mmol), and the mixture was then reacted at 50° C. for five hours. After completion of the reaction, a saturated aqueous sodium hydrogen carbonate solution was loaded to the polymerization solution to stop the reaction. This polymerization solution was added dropwise into a large amount of methanol to precipitate a polymerized product. The precipitated product was recovered, washed and dried to give 18.9 g of copolymer (P41) (yield: 94.7%).
Under a nitrogen atmosphere, a 100 mL pressure-resistant reaction vessel was loaded with methyl(phenyl)(vinyl)(4-vinylbenzyl)silane (7.6 g, 29.1 mmol) obtained in Synthesis Example 4, styrene (12.4 g, 119.2 mmol), toluene (20 g, 21.7 mmol), and a boron trifluoride-diethyl ether complex (0.36 g, 2.6 mmol), and the mixture was then reacted at 50° C. for five hours. After completion of the reaction, a saturated aqueous sodium hydrogen carbonate solution was loaded to the polymerization solution to stop the reaction. This polymerization solution was added dropwise into a large amount of methanol to precipitate a polymerized product. The precipitated product was recovered, washed and dried to give 17.8 g of copolymer (P51) (yield: 89.2%).
The reaction scheme is as follows:
Under a nitrogen atmosphere, a 100 mL pressure-resistant reaction vessel was loaded with methyl(phenyl)(vinyl)(4-vinylbenzyl)silane (5.8 g, 22.2 mmol) obtained in Synthesis Example 4, 4-tert-butylstyrene (14.2 g, 88.6 mmol), toluene (20 g, 21.7 mmol), and a boron trifluoride-diethyl ether complex (0.36 g, 2.6 mmol), and the mixture was then reacted at 50° C. for five hours. After completion of the reaction, a saturated aqueous sodium hydrogen carbonate solution was loaded to the polymerization solution to stop the reaction. This polymerization solution was added dropwise into a large amount of methanol to precipitate a polymerized product. The precipitated product was recovered, washed and dried to give 18.6 g of copolymer (P61) (yield: 93.2%).
The reaction scheme is as follows:
Under a nitrogen atmosphere, a 100 mL pressure-resistant reaction vessel was loaded with methyl(phenyl)(vinyl)(4-vinylbenzyl)silane (7.2 g, 27.5 mmol) obtained in Synthesis Example 4, indene (12.8 g, 110.2 mmol), toluene (20 g, 21.7 mmol), and a boron trifluoride-diethyl ether complex (0.36 g, 2.6 mmol), and the mixture was then reacted at 50° C. for five hours. After completion of the reaction, a saturated aqueous sodium hydrogen carbonate solution was loaded to the polymerization solution to stop the reaction. This polymerization solution was added dropwise into a large amount of methanol to precipitate a polymerized product. The precipitated product was recovered, washed and dried to give 19.0 g of copolymer (P71) (yield: 95.1%).
The reaction scheme is as follows:
Under a nitrogen atmosphere, a 100 mL pressure-resistant reaction vessel was loaded with dimethylvinylsilane A (dimethyl(vinyl)(4-vinylbenzyl)silane) (20 g, 98.8 mmol) obtained in Synthesis Example 1, toluene (20 g, 21.7 mmol), and a boron trifluoride-diethyl ether complex (0.36 g, 2.6 mmol), and the mixture was then reacted at 50° C. for five hours. After completion of the reaction, a saturated aqueous sodium hydrogen carbonate solution was loaded to the polymerization solution to stop the reaction. This polymerization solution was added dropwise into a large amount of methanol to precipitate a polymerized product. The precipitated product was recovered, washed and dried to give 16.8 g of homopolymer (P81) (yield: 83.8%).
The reaction scheme is as follows:
Under a nitrogen atmosphere, a 100 mL pressure-resistant reaction vessel was loaded with methyl(phenyl)(vinyl)(4-vinylbenzyl)silane (20 g, 76.5 mmol) obtained in Synthesis Example 4, toluene (20 g, 21.7 mmol), and a boron trifluoride-diethyl ether complex (0.36 g, 2.6 mmol), and the mixture was then reacted at 50° C. for five hours. After completion of the reaction, a saturated aqueous sodium hydrogen carbonate solution was loaded to the polymerization solution to stop the reaction. This polymerization solution was added dropwise into a large amount of methanol to precipitate a polymerized product. The precipitated product was recovered, washed and dried to give 17.9 g of homopolymer (P91) (yield: 89.3%).
The reaction scheme is as follows:
Table 1 shows the monomer composition and physical properties of each of the polymers obtained in Examples 11, 12, 21 to 25, 31, 41, 51, 61, 71, 81, and 91.
Curable polymer (P11), dicumyl peroxide (DCP) as a radical initiator and toluene were mixed in a mass ratio of 100:1:100 and stirred at room temperature to prepare a curable composition.
Next, the curable composition was applied onto a polyimide film with a thickness of 125 μm using an applicator (manufactured by YOSHIMITSU SEIKI) to form a 250 μm-thick coating film.
After heat-drying in an oven at 80° C. for 30 minutes in an air atmosphere, the coating film was heated under a nitrogen atmosphere at 200° C. for two hours to cause thermal curing of the coating film, thus obtaining a cured film product having a thickness of about 100 μm.
Table 2 shows the formulation composition excluding the solvent of the curable composition, and evaluation results of the resulting cured film product. The unit of the amount of formulation in the Table is “part(s) by mass”.
Curable polymer (P12), the following modified polyphenylene ether (PPE) oligomer (SA9000), dicumyl peroxide (DCP) as a radical initiator and toluene were mixed in a mass ratio of 50:50:1:100 and stirred at room temperature to prepare a curable composition. The resulting curable composition was used to produce a cured film product in the same manner as in Example 101.
(SA9000) Bifunctional methacrylic modified PPE oligomer (“SA9000” manufactured by SABIC) represented by the following formula:
Table 2 shows the formulation composition excluding the solvent of the curable composition, and evaluation results of the resulting cured film product.
Each curable composition was prepared and each cured film product was produced in the same manner as in Example 101 or Example 102 except that the type(s) and amounts of formulation of one or more type(s) of curable polymers were modified. Table 2 and Table 3 show the formulation composition excluding the solvent of the curable composition, and evaluation results of the resulting cured film product.
In Examples 101 to 115, a cured film product was obtained using a curable polymer as a copolymer containing a structural unit (UX) and a monovinyl aromatic compound-derived structural unit (UY).
In Example 121, a cured film product was obtained using a curable polymer as a homopolymer containing only a structural unit (UX) as a structural unit.
In Example 201, a cured film product was obtained using only a modified PPE oligomer containing no structural unit (UX).
In Examples 101 to 115 and 121, the dielectric dissipation factor (Df) under high-frequency conditions could be effectively reduced as compared with Example 201. In these Examples, it was possible to obtain a cured film product with effectively reduced dielectric dissipation factor (Df) under high-frequency conditions and sufficiently high glass transition temperature (Tg).
Curable polymer (P11) obtained in Example 11, dicumyl peroxide (DCP) as a radical initiator, spherical silica as an inorganic filler and toluene were mixed in a mass ratio of 100:1:100:100 and stirred at room temperature to prepare a curable composition (varnish).
The resulting curable composition (varnish) was impregnated into a glass cloth (E glass, #2116) as a fibrous substrate, followed by heating at 130° C. for five minutes to semi-cure the curable composition, thereby obtaining a prepreg.
Two sheets of the obtained prepreg were stacked and sandwiched between a pair of copper foils, and the resulting temporary multilayer body was heated and pressed under the conditions of 200° C., 1.5 hours, and 3 MPa to produce a metal clad laminate.
From the disclosure thus described, it will be obvious that the embodiments of the disclosure may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the disclosure, and all such modifications as would be obvious to one skilled in the art are intended for inclusion within the scope of the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2022-074066 | Apr 2022 | JP | national |
This application is based upon and claims the benefit of priority from Japanese patent application No. 2022-074066, filed on Apr. 28, 2022, and PCT application No. PCT/JP2023/016058 filed on Apr. 24, 2023, the disclosure of which is incorporated herein in its entirety by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2023/016058 | Apr 2023 | WO |
| Child | 18918199 | US |
