Polymer, resin composition, resin film, prepreg, adhesive sheet, laminate, and printed wiring board

Abstract

Provided are: a resin composition capable of forming a resin film having excellent adhesion to a metal (particularly a copper foil) and having a low dielectric loss tangent; a resin film, a prepreg, and an adhesive sheet formed using the resin composition; a laminate having the resin film or the prepreg; and a printed wiring board formed using the laminate. Also provided is a polymer capable of providing the resin composition. The polymer provided by the invention comprises a structural unit represented by the following formula (I), and at least one terminal of the polymer has a structure represented by the following formula (II). (In formula (I), R1-R4 each independently represent a hydrogen atom, an alkyl group having 1-10 carbon atoms, or an aryl group having 6-30 carbon atoms, m represents an integer of 0-3, and R1-R4 may bond to form a ring. ) (In formula (II), each R5 independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and n represents an integer of 1 to 30. > # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a polymer, a resin composition, a resin film, a prepreg, an adhesive sheet, a laminate, and a printed circuit board. Background Art

[0002] In recent years, with the high functionality and high performance of electronic devices such as smartphones and personal computers, there has been a demand for high functionality in components used in these electronic devices, such as circuit boards such as printed circuit boards for mounting semiconductor elements.

[0003] Specifically, in order to cope with the high speed of transmission signals required for the transmission and reception of high-definition and high-capacity moving images, etc., a circuit board (high-frequency circuit board) capable of suppressing signal delay and transmission loss in a high-frequency region at the level of several GHz is required. Moreover, in order to suppress signal delay and transmission loss, resin films such as interlayer insulating resin films used in high-frequency circuit boards are required to have electrical properties such as a low dielectric loss tangent. In addition, such a resin film is also required to be firmly adhered to a conductor such as a copper foil in the circuit board (i.e., excellent adhesion).

[0004] In order to meet such requirements, for example, Patent Document 1 proposes a resin film formed using a resin composition containing a cyclic olefin resin having a silyl group on a side chain and an acid generator.

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2006-104223. Summary of the Invention

[0008] Problems to be Solved by the Invention

[0009] However, the resin composition of the above prior art still has room for improvement in terms of improving the adhesion of the obtained resin film to a metal (especially a copper foil) and reducing the dielectric loss tangent of the resin film.

[0010] Therefore, an object of the present invention is to provide a resin composition capable of forming a resin film having excellent adhesion to a metal (especially a copper foil) and a low dielectric loss tangent, a resin film formed using the resin composition, a prepreg, and an adhesive sheet, a laminate having the resin film or the prepreg, and a printed circuit board formed using the laminate. In addition, an object of the present invention is to provide a polymer capable of providing the above resin composition.

[0011] Means for Solving the Problems

[0012] The present inventors have conducted intensive studies for the purpose of solving the above problems. Then, the present inventors have newly found that a resin composition containing a specific polymer having a specific silyl group at the end of the main chain can improve the adhesion of the resulting resin film to a metal (especially a copper foil) while reducing the dielectric loss tangent of the resin film, thereby completing the present invention.

[0013] That is, an object of the present invention is to advantageously solve the above problems, and the present invention provides: [1] A polymer comprising a structural unit represented by the following formula (I), and at least one end of the polymer having a structure represented by the following formula (II),

[0014] [Chemical formula 1]

[0015]

[0016] (In formula (I), R1 to R4 each independently represent a hydrogen atom, an alkyl group having 1 or more and 10 or less carbon atoms, or an aryl group having 6 or more and 30 or less carbon atoms, m represents an integer of 0 to 3, and R1 to R4 can bond to form a ring),

[0017] [Chemical formula 2]

[0018]

[0019] (In formula (II), each R5 independently represents a linear or branched alkyl group having 1 or more and 10 or less carbon atoms, or an alkoxy group having 1 or more and 10 or less carbon atoms, and n represents an integer of 1 to 30).

[0020] As such, if the above polymer is used, a resin composition capable of obtaining a resin film having excellent adhesion to a metal (especially a copper foil) and a low dielectric loss tangent can be obtained.

[0021] Furthermore, an object of the present invention is to advantageously solve the above problems, and the present invention provides:

[0022] [2] A resin composition comprising the polymer of the above [1]. As such, if a resin composition containing the above polymer is used, a resin film having excellent adhesion to a metal (especially a copper foil) and a low dielectric loss tangent can be obtained.

[0023] [3] The resin composition of the above [2] preferably further contains a crosslinking agent. As such, if the resin composition contains a crosslinking agent, excellent chemical resistance, mechanical properties, and heat resistance can be imparted to the resin film by subjecting the resulting resin film to a crosslinking treatment.

[0024] [4] In the resin composition of [3] above, it is preferable that the crosslinking agent contains a compound having an unsaturated bond. If the crosslinking agent contains a compound having an unsaturated bond in this way, by subjecting the obtained resin film to a crosslinking treatment, more excellent chemical resistance, mechanical properties, and heat resistance can be imparted to the resin film.

[0025] [5] In the resin composition of [3] or [4] above, it is preferable that the crosslinking agent contains a peroxide. If the crosslinking agent contains a peroxide in this way, chemical resistance, mechanical properties, and heat resistance can be improved at a lower curing temperature.

[0026] Furthermore, an object of the present invention is to advantageously solve the above problems, and the present invention is: [6] A resin film formed by using the resin composition described in any one of [2] to [5] above. In this way, the resin film formed by using any of the above resin compositions has excellent adhesion to a metal (especially a copper foil) and a low dielectric loss tangent.

[0027] Furthermore, an object of the present invention is to advantageously solve the above problems, and the present invention is: [7] A prepreg composed of a fiber base material and the resin composition of any one of [2] to [5] above. In this way, the prepreg containing any of the above resin compositions has excellent adhesion to a metal (especially a copper foil) and a low dielectric loss tangent.

[0028] Furthermore, an object of the present invention is to advantageously solve the above problems, and the present invention is: [8] An adhesive sheet comprising: a carrier film and a resin film formed on one surface of the carrier film, the resin film being obtained by using the resin composition described in any one of [2] to [5] above. In this way, by using the adhesive sheet, a laminate having excellent adhesion of the resin film to a metal (especially a copper foil) and a low dielectric loss tangent can be obtained, and the adhesive sheet contains a resin film formed by using any of the above resin compositions.

[0029] Furthermore, an object of the present invention is to advantageously solve the above problems, and the present invention is: [9] A laminate having a copper foil and the resin film of [6] above. In this way, the laminate having the above resin film has excellent adhesion between the copper foil and the resin film and a low dielectric loss tangent.

[0030] Furthermore, an object of the present invention is to advantageously solve the above problems, and the present invention is:

[10] A printed circuit board formed by using the laminate of [9] above. In this way, the printed circuit board formed by using the above laminate can be particularly preferably used as a high-frequency printed circuit board because it has excellent adhesion between the copper foil and the resin layer and a low dielectric loss tangent.

[0031] In addition, an object of the present invention is to advantageously solve the above problems, and the present invention provides:

[11] A laminate having a copper foil and the prepreg of [7] above. Such a laminate having the above prepreg has excellent adhesion between the copper foil and the prepreg and a low dielectric loss tangent.

[0032] In addition, an object of the present invention is to advantageously solve the above problems, and the present invention provides:

[12] A printed circuit board as described above, which is formed using the laminate of

[11] above. Such a printed circuit board formed using the above laminate has excellent adhesion between the copper foil and the prepreg and a low dielectric loss tangent, and thus can be particularly preferably used as a high-frequency printed circuit board.

[0033] Advantages of the Invention

[0034] According to the present invention, it is possible to provide a resin composition capable of forming a resin film having excellent adhesion to a metal (especially a copper foil) and a low dielectric loss tangent, a resin film formed using the resin composition, a prepreg and a bonding sheet, a laminate having the resin film or the prepreg, and a printed circuit board formed using the laminate. In addition, according to the present invention, it is possible to provide a polymer capable of forming the above resin composition. Detailed Embodiments

[0035] Hereinafter, embodiments of the present invention will be described.

[0036] Here, the polymer of the present invention can be preferably used, for example, in the preparation of the resin composition of the present invention. The resin composition of the present invention can be preferably used when forming a resin film, a prepreg, and a bonding sheet that can be used in, for example, electronic components such as integrated circuit elements, organic EL elements, and semiconductor packages. The resin film of the present invention can be preferably used as, for example, the resin film that can be used in the above electronic components. The prepreg of the present invention can be preferably used as, for example, the prepreg that can be used in the above electronic components. The bonding sheet of the present invention can be preferably used, for example, in the manufacture of the laminate of the present invention. Moreover, the laminate of the present invention can be preferably used as a material for manufacturing, for example, the printed circuit board of the present invention.

[0037] (Polymer)

[0038] The polymer of the present invention is a component that can improve the adhesion of a resin film containing the polymer to a metal (especially a copper foil) while reducing the dielectric loss tangent of the resin film. Moreover, the polymer in the present invention is characterized in that it contains a structural unit (repeating unit) represented by the following formula (I), and at least one end of the polymer has a structure represented by the following formula (II). In addition, the polymer can optionally contain other structural units (repeating units) in addition to the structural unit represented by formula (I).

[0039] [Chemical Formula 3]

[0040]

[0041] [Chemical Formula 4]

[0042]

[0043] <Structural unit represented by formula (I)>

[0044] In the structural unit represented by formula (I), R1 to R4 each independently represent a hydrogen atom, an alkyl group having 1 or more and 10 or less carbon atoms, or an aryl group having 6 or more and 30 or less carbon atoms, m represents an integer of 0 to 3, and R1 to R4 can bond to form a ring.

[0045] Here, the alkyl group having 1 or more and 10 or less carbon atoms that can constitute R1 to R4 is not particularly limited, and examples thereof include unsubstituted alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, hexyl, octyl, nonyl, and decyl. Among them, methyl and ethyl are preferred.

[0046] The aryl group having 6 or more and 30 or less carbon atoms that can constitute R1 to R4 is not particularly limited, and examples thereof include phenyl and naphthyl. Among them, phenyl is preferred.

[0047] The ring formed by the bonding of R1 to R4 can be a monocyclic ring or a polycyclic ring. The ring formed by the bonding of R1 to R4 is not particularly limited, and examples thereof include aromatic or non-aromatic hydrocarbon rings, and polycyclic condensed rings formed by the condensation of two or more of these rings.

[0048] In formula (I), m represents an integer of 0 to 3, and is preferably 0 or 1.

[0049] As a specific example of the structural unit represented by formula (I), for example, a structural unit derived from a "norbornene-based monomer" described later can be mentioned.

[0050] Among them, as the structural unit represented by formula (I), preferred are: a structural unit in which m is 0 and R1 to R4 bond to form a ring structure; a structural unit in which m is 0 and one of R1 to R4 is an alkyl group having 1 or more and 10 or less carbon atoms and the rest are hydrogen atoms; and a structural unit in which m is 1 and one of R1 to R4 is an alkyl group having 1 or more and 10 or less carbon atoms and the rest are hydrogen atoms. More preferably: a structural unit in which m is 0 and R1 to R4 bond to form an indane ring; a structural unit in which m is 0, R1 to R3 are hydrogen atoms, and R4 is an ethyl group; and a structural unit in which m is 1, R1 to R3 are hydrogen atoms, and R4 is an ethyl group.

[0051] Moreover, when the proportion of all repeating units in the polymer is set to 100 mol%, the proportion of the structural unit represented by formula (I) in the polymer is preferably 85 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and particularly preferably 100 mol%. If the proportion of the structural unit represented by formula (I) in the polymer is within the above range, it is possible to further improve the adhesion of the resulting resin film to a metal (especially a copper foil) while further reducing the dielectric loss tangent of the resin film.

[0052] In addition, in the present invention, the "proportion of structural units" or "proportion of structures" can be measured using 1 H-NMR, 13 C-NMR, 29 Si-NMR and other nuclear magnetic resonance (NMR) methods.

[0053] <Structure represented by formula (II)>

[0054] In the structure represented by formula (II), in the above formula (II), each R5 independently represents a linear or branched alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. Here, in formula (II), the three R5s may be the same or different from each other. From the viewpoint of further improving the adhesion of the resulting resin film to a metal (especially a copper foil) while further reducing the dielectric loss tangent of the resin film, it is preferred that at least one of the three R5s is an alkoxy group, and more preferably all are alkoxy groups.

[0055] The linear or branched alkyl group having 1 to 10 carbon atoms that can form R5 is not particularly limited, and examples thereof include the same ones as those alkyl groups that can form R1 to R4 described above. Among them, methyl and ethyl are preferred.

[0056] In addition, the alkoxy group having 1 to 10 carbon atoms that can form R5 is not particularly limited, and it may be linear or branched, and examples thereof include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, and octoxy group. Among them, an alkoxy group having 1 to 6 carbon atoms is preferred, more preferably methoxy group or ethoxy group, and still more preferably methoxy group.

[0057] Furthermore, in formula (II), n represents an integer of 1 to 30, preferably an integer of 2 or more, more preferably an integer of 4 or more, and still more preferably an integer of 6 or more. The larger n is, the more it is possible to further improve the adhesion of the resulting resin film to a metal (especially a copper foil) while further reducing the dielectric loss tangent of the resin film.

[0058] As the structure represented by formula (II), a structure in which all R5 in formula (II) are alkoxy groups having 1 to 10 carbon atoms and n is an integer of 2 or more is preferred, and a structure in which all R5 are methoxy or ethoxy groups and n is 2 or more is more preferred.

[0059] As described above, at least one end of the main chain of the polymer has a structure represented by formula (II). Thus, it is possible to improve the adhesion of the obtained resin film to a metal (especially a copper foil) while reducing the dielectric loss tangent of the resin film.

[0060] In the case where both ends of the main chain have a structure represented by formula (II), the two structures represented by formula (II) may be the same or different from each other.

[0061] Moreover, when the proportion of all repeating units in the polymer other than the structure represented by formula (II) is set to 100 mol%, the proportion of the structure represented by formula (II) in the polymer is preferably 1 mol% or more, more preferably 1.5 mol% or more, preferably 10 mol% or less, and more preferably 5 mol% or less. If the proportion of the structure represented by formula (II) in the polymer is within the above range, it is possible to further improve the adhesion of the obtained resin film to a metal (especially a copper foil) while further reducing the dielectric loss tangent of the resin film.

[0062] Here, the method for introducing the structure represented by formula (II) into at least one end of the main chain of the polymer is not particularly limited, and examples thereof include a method of subjecting a monomer composition containing a norbornene-based monomer capable of forming a structural unit represented by formula (I) to ring-opening polymerization in the presence of a compound capable of forming the structure represented by formula (II) as a chain transfer agent (molecular weight regulator).

[0063] As the compound capable of forming the structure represented by formula (II), for example, a compound represented by CHX=CHSi(R6)3, CH2=CHSi(R6)3, CH2=CH(CH2) n Si(R6)3 (wherein X represents a halogen atom, each R6 independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and n represents an integer of 1 to 29) can be used.

[0064] As specific examples of the above compounds, for example, dimethylmethoxyvinylsilane, dimethylethoxyvinylsilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, trimethoxy(7-octen-1-yl)silane, triethoxy(7-octen-1-yl)silane, etc. can be cited. In addition, one of these compounds can be used, or two or more thereof can be used in combination.

[0065] That is, as specific examples of the structure represented by formula (II), for example, -(CH2)1Si(OMe)2(Me), -(CH2)1Si(OEt)2(Me), -(CH2)1Si(OMe)(Me)2, -(CH2)1Si(OEt)(Me)2, -(CH2)1Si(OMe)3, -(CH2)1Si(OEt)3, -(CH2)2Si(OMe)3, -(CH2)2Si(OEt)3, -(CH2)7Si(OMe)3, -(CH2)7Si(OEt)3, etc. can be cited. In addition, Me represents a methyl group, and Et represents an ethyl group.

[0066] <Other structural units>

[0067] As other structural units (repeating units) that the polymer can optionally contain, there is no particular limitation, and for example, structural units derived from norbornene-based compounds can be cited.

[0068] As norbornene compounds that can form structural units derived from norbornene compounds, there is no particular limitation, and for example, monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, 1,4-cyclooctadiene, cyclodecene, etc. can be cited. One of the above norbornene compounds can be used, or two or more thereof can be used in combination.

[0069] Moreover, when the proportion of all repeating units in the polymer is set to 100 mol%, the proportion of other structural units (total proportion of other structural units) is usually 0 mol% or more and 10 mol% or less.

[0070] <Properties of the polymer>

[0071] [Weight-average molecular weight]

[0072] The weight-average molecular weight (Mw) of the above polymer is preferably 5000 or more, more preferably 10000 or more, preferably 500000 or less, more preferably 300000 or less, and further preferably 100000 or less. If the weight-average molecular weight of the polymer is above the above lower limit, the mechanical properties can be improved. In addition, if the weight-average molecular weight of the polymer is below the above upper limit, the solvent solubility can be improved.

[0073] In the present invention, the weight-average molecular weight of the polymer can be measured according to the method described in the examples.

[0074] [Molecular weight distribution]

[0075] The molecular weight distribution (Mw / Mn) of the above polymer is preferably 1.5 or more and preferably 3 or less. If the molecular weight distribution of the polymer is within the above range, a decrease in the mechanical strength and an increase in the melt viscosity of the polymer can be suppressed. In addition, in the present invention, "molecular weight distribution (Mw / Mn)" means the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn). Further, in the present invention, the number-average molecular weight of the polymer can be measured according to the method described in the examples.

[0076] <Manufacturing method of polymer>

[0077] The manufacturing method of the above polymer is not particularly limited, and the above polymer can be efficiently manufactured by the following method, which includes: a step of subjecting a monomer composition containing a norbornene monomer capable of forming a structural unit represented by formula (I) to ring-opening polymerization in the presence of a compound capable of forming a structure represented by formula (II) as a chain transfer agent to obtain a ring-opening polymer (ring-opening polymerization step); and a step of subjecting the obtained ring-opening polymer to a hydrogenation reaction to obtain a hydrogenated ring-opening polymer (hydrogenation step).

[0078] In addition, the above polymer manufactured by the above manufacturing method can include: a polymer having a structural unit represented by formula (II) at only one end; a polymer having structural units represented by formula (II) at both ends; and a polymer having no structural unit represented by formula (II) at both ends.

[0079] [Ring-opening polymerization step]

[0080] In the ring-opening polymerization step, in the presence of the compound capable of forming a structure represented by formula (II), the monomer composition containing a norbornene monomer capable of forming a structural unit represented by formula (I) is subjected to ring-opening polymerization to produce a ring-opening polymer. Here, as the compound capable of forming a structure represented by formula (II), those described in the "polymer" item can be used.

[0081] - Norbornene monomer -

[0082] As the above norbornene monomer, there is no particular limitation as long as the structural unit represented by formula (I) can be obtained, and for example, tetracyclo[4.4.0.1 2,5 .1 7,10Dodec-3-ene (common name: tetracyclododecene), 8-ethylidene-tetracyclo[4.4.0.1 2,5 .1 7,10 Dodec-3-ene (common name: ethylidene tetracyclododecene), tricyclo[5.2.1.0 2 ,6 Deca-3,8-diene (common name: dicyclopentadiene), 1,4-methano-1,4,4a,9a-tetrahydrofluorene (common name: methano tetrahydrofluorene), 5-ethylidene bicyclo[2.2.1]hept-2-ene (common name: ethylidene norbornene), bicyclo[2.2.1]hept-2-ene (also known as "norbornene"), 5-ethyl-bicyclo[2.2.1]hept-2-ene, 5-butyl-bicyclo[2.2.1]hept-2-ene, 5-methylene-bicyclo[2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-2-ene, tetracyclo[10.2.1.0 2,11 .0 4,9 Pentadec-4,6,8,13-tetraene, 9-methyl-tetracyclo[6.2.1.1 3,6 .0 2,7 Dodec-4-ene, 9-ethyl-tetracyclo[6.2.1.1 3,6 .0 2,7 Dodec-4-ene, 9-methylene-tetracyclo[6.2.1.1 3,6 .0 2,7 Dodec-4-ene, 9-ethylidene-tetracyclo[6.2.1.1 3,6 .0 2 ,7 Dodec-4-ene, 9-vinyl-tetracyclo[6.2.1.1 3,6 .0 2,7 Dodec-4-ene, 9-propenyl-tetracyclo[6.2.1.1 3 ,6 .0 2,7 Dodec-4-ene, pentacyclo[9.2.1.1 3,9 .0 2,10 .0 4,8 Pentadec-5,12-diene, 9-phenyl-tetracyclo[6.2.1.1 3,6 .0 2,7 Dodec-4-ene, tetracyclo[9.2.1.0 2,10 .0 3,8 Tetradec-3,5,7,12-tetraene, pentacyclo[9.2.1.1 3,9 .0 2,10 .0 4,8Pentadec-12-ene and their derivatives, etc. In addition, derivatives refer to those having substituents in the ring structure. Moreover, as substituents that can be present in the ring structure, examples include alkyl groups, alkylene groups, vinyl groups, alkoxycarbonyl groups, and alkylidene groups. Further, the ring structure of the derivative can have one of these substituents or two or more of them.

[0083] These norbornene-based monomers can be used alone or in combination of two or more.

[0084] Among them, from the viewpoint of further improving the adhesion of the obtained resin film to metals (especially copper foil) while further reducing the dielectric loss tangent of the resin film, methylene tetrahydrofluorene, ethylidene norbornene, and ethylidene tetracyclododecene are preferred, and methylene tetrahydrofluorene is more preferred.

[0085] The ring-opening polymerization reaction can be carried out in a solvent in the presence of a compound capable of forming a structure represented by formula (II) as a chain transfer agent according to a known method. As the solvent, there is no particular limitation, and organic solvents such as anisole, tetrahydrofuran, and toluene can be used. In addition, as the ring-opening polymerization catalyst, a metal catalyst containing metals such as molybdenum, tungsten, and ruthenium can be used, and among them, a ruthenium-containing metal catalyst such as benzylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloride(tricyclohexylphosphine)ruthenium is preferred.

[0086] The amount of the compound capable of forming a structure represented by formula (II) as the chain transfer agent is not particularly limited, and is preferably 1 mole or more, more preferably 1.5 moles or more, preferably 10 moles or less, and more preferably 5 moles or less relative to 100 moles of the monomer composition containing the above norbornene-based monomers.

[0087] In addition, the ring-opening polymerization time is usually 1 hour or more and 10 hours or less, preferably 2 hours or more and 5 hours or less. Moreover, the ring-opening polymerization temperature is usually 20°C or more and 100°C or less, preferably 90°C or less.

[0088] [Hydrogenation process]

[0089] In the hydrogenation process, a hydrogenation reaction is carried out on the ring-opening polymer obtained in the ring-opening polymerization process to synthesize a hydrogenated ring-opening polymer.

[0090] At this time, the hydrogenation reaction can be carried out according to a well-known method. In addition, the hydrogenation reaction time, hydrogenation reaction temperature, and hydrogenation pressure in the hydrogenation reaction are not particularly limited. The hydrogenation reaction time is usually 1 hour or more and 10 hours or less, preferably 5 hours or less. In addition, the hydrogenation reaction temperature is usually 100°C or more and 200°C or less, preferably 180°C or less. Moreover, the hydrogenation pressure is usually 1 MPa or more and 20 MPa or less, preferably 10 MPa or less.

[0091] In addition, hydrogenation is preferably carried out in such a manner that the hydrogenation rate (the proportion of carbon-carbon double bonds hydrogenated among the non-aromatic carbon-carbon unsaturated bonds present in the ring-opening polymer) of non-aromatic carbon-carbon unsaturated bonds such as vinyl double bonds present in the ring-opening polymer is 90% or more, more preferably 95% or more, and further preferably 98% or more.

[0092] (Resin composition)

[0093] The resin composition of the present invention contains the polymer of the present invention described above, and optionally contains at least one selected from crosslinking agents, solvents, and other additive components. Moreover, when the resin composition of the present invention is used, a resin film having excellent adhesion to a metal (especially a copper foil) and a low dielectric loss tangent can be formed.

[0094] <Crosslinking agent>

[0095] The resin composition of the present invention preferably contains a crosslinking agent. When the resin composition contains a crosslinking agent, a crosslinkable resin film can be obtained. Moreover, by performing crosslinking (curing) treatment such as heating or energy beam irradiation on the resin film, a crosslinked structure can be formed in the resin film, and a resin film (cured resin film) having excellent chemical resistance and the like can be obtained.

[0096] The crosslinking agent is not particularly limited, and examples thereof include radical generators such as peroxides and compounds having an unsaturated bond. They can be used alone or in combination of two or more.

[0097] From the viewpoint of further improving the chemical resistance, mechanical strength, and heat resistance of the obtained resin film (cured resin film), the crosslinking agent preferably contains a peroxide or a compound having an unsaturated bond, more preferably contains a peroxide and a compound having an unsaturated bond, and further preferably consists of a peroxide and a compound having an unsaturated bond.

[0098] Examples of the peroxide include hydroperoxides such as tert-butyl hydroperoxide, p-menthane hydroperoxide, and cumene hydroperoxide; dialkyl peroxides such as dicumyl peroxide, tert-butyl cumyl peroxide, α,α'-bis(tert-butylperoxy-m-isopropyl)benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)-3-hexyne, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane; diacyl peroxides such as dipropionyl peroxide and benzoyl peroxide; ketone peroxides such as 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hex-3-yne, and 1,3-bis(tert-butylperoxyisopropyl)benzene; peresters such as tert-butyl peroxyacetate and tert-butyl peroxybenzoate; percarbonates such as tert-butyl trimethylsilyl peroxide and bis(peroxyisopropyl)dicarbonate; and alkylsilyl peroxides such as tert-butyltrimethylsilyl peroxide. Among them, dialkyl peroxides are preferred, and dicumyl peroxide is more preferred.

[0099] The compound having an unsaturated bond is not particularly limited, and examples thereof include a compound having an allyl group, a compound having a maleimide group, a compound having a (meth)acryloyl group, a compound having a styryl group, and a compound having a vinyl group. In addition, in the present specification, the “(meth)acryloyl group” means an acryloyl group and / or a methacryloyl group.

[0100] Examples of the compound having an allyl group include diallyl ether, tetraallyloxyethane, pentaerythritol triallyl ether, 9,9-bis(4-allyloxyphenyl)fluorene, diallyl adipate, triallyl 1,3,5-benzenetricarboxylate, triallyl cyanurate, diallylpropyl isocyanurate, triallyl isocyanurate, and isocyanuric acid derivatives (for example, L-DAIC, DD-1, P-DAIC manufactured by Shikoku Chemicals Corporation).

[0101] Examples of the compound having a maleimide group include 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, maleimide resins such as “MIZ-001” manufactured by Nippon Kayaku Co., Ltd., diallyl nadimide such as “BANI-M” and “BANI-X” manufactured by Maruzen Petrochemical Co., Ltd., and the compound represented by the following formula (III) (circulated as “MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd.).

[0102] Examples of the compound having a (meth)acryloyl group include 1,6 - hexanediol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, tris(2 - acryloyloxyethyl) isocyanurate, bisphenol A dimethacrylate, polybutadiene terminal diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., "BAC - 45"), polyphenylene ether having a methacryloyl group (manufactured by Saudi Basic Industries (SABIC) Corporation, "Noryl (registered trademark) SA9000"), etc.

[0103] Examples of the compound having a styryl group include 1,2 - divinylbenzene, 1,3 - divinylbenzene, 1,4 - divinylbenzene, and the compound represented by the following formula (IV) (manufactured by Mitsubishi Gas Chemical Company, Inc., distributed as "OPE - 2St1200" and "OPE - 2St2200"), etc.

[0104] Examples of the compound having a vinyl group include 1,4 - butanediol divinyl ether, cyclohexanedimethanol divinyl ether, cyclohexanedimethanol divinyl ether, 1,2 - polybutadiene (manufactured by Nippon Soda Co., Ltd., B - 1000, B - 2000, B - 3000), partially hydrogenated 1,2 - polybutadiene (manufactured by Nippon Soda Co., Ltd., B - 3015), styrene - butadiene - styrene block polymer (manufactured by Nippon Soda Co., Ltd., 1,2 - SBS), 2,4,6 - trimethyl - 2,4,6 - trivinylcyclotrisiloxane, etc.

[0105] In addition, these compounds can be used alone or in combination of two or more.

[0106] Among these, compounds having an allyl group are preferred, triallyl isocyanurate or isocyanuric acid derivatives are more preferred, and triallyl isocyanurate is further preferred.

[0107] [Chemical formula 5]

[0108]

[0109] In formula (III), a is an integer of 1 or more and 30 or less, preferably an integer of 1 or more and 20 or less, more preferably an integer of 1 or more and 10 or less.

[0110] [Chemical formula 6]

[0111]

[0112] In formula (IV), b and c are each independently an integer of 0 or more and 300 or less. However, the case where either b or c is 0 is excluded.

[0113] The compounding ratio of the crosslinking agent is not particularly limited and can be appropriately set. From the viewpoint of further improving the chemical resistance, mechanical strength, and heat resistance of the obtained resin film, the compounding ratio of the crosslinking agent relative to 100 parts by mass of the polymer is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, preferably 100 parts by mass or less, and more preferably 50 parts by mass or less.

[0114] The compounding ratio of the compound having an unsaturated bond is not particularly limited. From the viewpoint of further improving the chemical resistance, mechanical strength, and heat resistance of the obtained resin film, the compounding ratio of the compound having an unsaturated bond relative to 100 parts by mass of the polymer is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, preferably 100 parts by mass or less, and more preferably 50 parts by mass or less.

[0115] The compounding ratio of the peroxide is not particularly limited. From the viewpoint of further improving the adhesion of the obtained resin film to a metal (especially a copper foil), further reducing the dielectric loss tangent of the resin film, and improving the chemical resistance, mechanical strength, and heat resistance at a lower curing temperature, the compounding ratio of the peroxide relative to 100 parts by mass of the polymer is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, preferably less than 8 parts by mass, and more preferably 5 parts by mass or less.

[0116] <Solvent>

[0117] The solvent that can be contained in the resin composition of the present invention is not particularly limited, and examples thereof include aromatic solvents such as anisole, toluene, o-xylene, m-xylene, p-xylene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, and tetralin; hydrocarbons such as cyclohexane and decalin; ether solvents such as dibutyl ether, diisopentyl ether, tetrahydrofuran, and cyclopentyl methyl ether; ester solvents such as butyl acetate, hexyl acetate, and propylene glycol monomethyl ether acetate; and ketone solvents such as methyl ethyl ketone, diisobutyl ketone, and cyclopentanone. These solvents can be used alone or in combination of two or more.

[0118] Moreover, regarding the content of the solvent in the resin composition, the amount of the total mass excluding the solvent relative to the total mass of the resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, preferably 60% by mass or less, and more preferably 50% by mass or less.

[0119] <Other Additive Components>

[0120] In addition, other additive components that can be included in the resin composition of the present invention are not particularly limited, and examples thereof include surfactants, antioxidants, organic fillers, inorganic fillers, flame retardants, and the like. These additive components can be used alone or in combination of two or more. As long as the effects of the present invention are not impaired, the proportion of other additive components in the resin composition is not particularly limited and can be appropriately set according to the type of additive component.

[0121] From the viewpoint of improving the coatability of the resin composition of the present invention and further improving the uniformity of the film thickness of the obtained resin film, the resin composition particularly preferably contains a surfactant as an additive component.

[0122] The surfactant is not particularly limited, and known silicone-based surfactants, fluorine-based surfactants, etc. can be used.

[0123] Moreover, the proportion of the surfactant in the resin composition is not particularly limited, and is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, based on the total mass of the resin composition.

[0124] The antioxidant is not particularly limited, and known antioxidants can be used. Examples of the antioxidant include phenolic compounds such as 2,6-di-tert-butyl-p-cresol (BHT); phosphoric acid compounds such as tris(nonylphenyl) phosphite; sulfur-based compounds such as dilauryl thiodipropionate and other dialkyl esters of thiodipropionic acid.

[0125] Moreover, the proportion of the antioxidant in the resin composition is not particularly limited, and is preferably 5% by mass or less, more preferably 3% by mass or less, based on the total mass of the resin composition.

[0126] The inorganic filler is not particularly limited, and examples thereof include inorganic fillers that can improve the heat resistance and flame retardancy of the cured product of the resin composition. Specifically, examples include silica, alumina, talc, aluminum hydroxide, magnesium hydroxide, titanium oxide, mica, aluminum borate, barium sulfate, and calcium carbonate. In addition, these inorganic fillers can be used directly, but inorganic fillers surface-treated with a vinylsilane type, styrylsilane type, methacryl group silane type, or acrylic silane type silane coupling agent are particularly preferred. These can be used alone or in combination of two or more. A laminate having a resin film obtained by using the following resin composition tends to have higher heat resistance when absorbing moisture and also higher interlayer peeling strength. The above resin composition is blended with such an inorganic filler surface-treated with a silane coupling agent.

[0127] Moreover, the proportion of the inorganic filler in the resin composition is not particularly limited, and is preferably 5 to 60% by mass, more preferably 10 to 60% by mass, and still more preferably 15 to 50% by mass relative to the total mass of the resin composition.

[0128] The flame retardant is not particularly limited, and known flame retardants can be used. Specifically, examples of the flame retardant include halogen-based flame retardants such as bromine-based flame retardants, and phosphorus-based flame retardants. Specific examples of the halogen-based flame retardants include bromine-based flame retardants such as pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A, and hexabromocyclododecane, and chlorine-based flame retardants such as chlorinated paraffin. In addition, specific examples of the phosphorus-based flame retardants include phosphate esters such as condensed phosphate esters and cyclic phosphate esters, phosphazene compounds such as cyclic phosphazene compounds, phosphonate-based flame retardants such as aluminum dialkylphosphonate salts and other phosphonate salts, and melamine-based flame retardants such as melamine phosphate and melamine polyphosphate. These can be used alone or in combination of two or more.

[0129] <Preparation Method of Resin Composition>

[0130] The resin composition of the present invention can be prepared, for example, by mixing the polymer of the present invention described above with any of the above components (crosslinking agent, solvent, and / or other additive components) by a known method, and optionally filtering the resulting mixture. Mixing can be carried out using known mixers such as stirrers, ball mills, sand mills, bead mills, pigment dispersers, grinders, ultrasonic dispersers, homogenizers, planetary mixers, Filmix, etc. In addition, filtration can be carried out by a usual filtration method using a filter medium such as a filter.

[0131] (Resin Film)

[0132] The resin film of the present invention is formed using the resin composition of the present invention described above. Specifically, the resin film of the present invention is usually formed by film-forming the solid components (parts other than the solvent) of the resin composition of the present invention described above. That is, the resin film of the present invention contains the above polymer and optionally contains at least one selected from crosslinking agents and other additive components. Therefore, the resin film of the present invention has excellent adhesion to metals (especially copper foils) and a low dielectric loss tangent. Therefore, the resin film of the present invention can preferably be used as, for example, an insulating film (film) or an adhesive layer in a circuit board that requires suppression of signal delay and transmission loss.

[0133] In addition, when the resin film is formed using a resin composition containing a crosslinking agent (i.e., in the case of a crosslinkable resin film), the resin film of the present invention can be subjected to a crosslinking treatment such as heating to form a cured film (film). Such a resin film has an excellent chemical resistance, mechanical strength, and heat resistance due to its crosslinked structure. The crosslinking treatment can be carried out by heating or the like, for example, by heating during the production of the laminate described later.

[0134] <Thickness>

[0135] The thickness of the resin film can be appropriately selected according to the use, and can be, for example, 3 μm or more and 50 μm or less.

[0136] <Dielectric loss tangent>

[0137] The dielectric loss tangent of the resin film of the present invention is preferably less than 0.002, and more preferably 0.0015 or less. If the dielectric loss tangent is less than the above upper limit value, when the resin film of the present invention is used for a circuit board, signal delay and transmission loss can be well suppressed.

[0138] In addition, in the present invention, the dielectric loss tangent can be measured by the method described in the examples.

[0139] <Adhesion to copper foil>

[0140] The adhesion strength of the resin film of the present invention to the copper foil is preferably 8.0 N / cm or more, and more preferably 9.0 N / cm or more. If the adhesion strength to the copper foil is the above lower limit value or more, the adhesion of the resin film to the copper foil is excellent.

[0141] In addition, in the present invention, the adhesion strength of the resin film to the copper foil can be measured by the method described in the examples.

[0142] <Adhesion to prepreg>

[0143] The adhesion strength of the resin film of the present invention to the prepreg is preferably 8.0 N / cm or more, and more preferably 9.0 N / cm or more. If the adhesion strength to the prepreg is the above lower limit value or more, the adhesion of the resin film to the prepreg is excellent. Here, the prepreg is usually formed by impregnating a fiber base material with a resin composition containing a solvent and then optionally heating and drying. Examples of the prepreg include the prepreg of the present invention described later.

[0144] In addition, in the present invention, the adhesion strength of the resin film to the prepreg can be measured by the method described in the examples.

[0145] The resin film can be manufactured by coating a resin composition on a substrate so as to form a specified thickness, and then optionally removing the solvent by heating and drying. The coating method is not particularly limited, and any coating device such as a die coater or a rod coater can be used for coating.

[0146] The substrate for coating the resin composition is not particularly limited, and examples thereof include substrates obtained by subjecting known synthetic resin sheets, papers, cloths, and non-woven fabrics to a release treatment; metal foils such as copper foils.

[0147] That is, the resin film of the present invention can be in the form of a resin film with a substrate as a support, and can be peeled off from the substrate when in use. Such a resin film with a substrate can preferably be used as, for example, the adhesive sheet of the present invention described below.

[0148] (Prepreg)

[0149] The prepreg of the present invention is composed of a fibrous substrate and the resin composition of the present invention described above. Specifically, the prepreg of the present invention is usually formed by impregnating a fibrous substrate with the resin composition of the present invention containing a solvent, and then optionally heating and drying. Moreover, since the prepreg of the present invention contains the resin composition of the present invention, it has excellent adhesion to metals (especially copper foils) and a low dielectric loss tangent.

[0150] Here, as the fibrous substrate, known ones can be used, and examples thereof include inorganic fibers other than glass such as glass fibers and quartz; organic fibers such as polyimide, polyamide, and polyester; woven fabrics such as liquid crystal polyester. As the shape of the fibrous substrate, woven fabrics, non-woven fabrics, rovings, chopped mats, and surface mats are known, and any of them can be used. These can be used alone or in combination of two or more.

[0151] The thickness of the fibrous substrate is not particularly limited, and is preferably 15 μm or more and 300 μm or less. In addition, the thickness of the prepreg is not particularly limited, and is preferably 15 μm or more and 300 μm or less.

[0152] Furthermore, the content ratio of the resin composition (solid content) in the prepreg is not particularly limited, and is preferably 10% by mass or more and 80% by mass or less relative to the total amount of the prepreg.

[0153] (Adhesive sheet)

[0154] The adhesive sheet of the present invention is composed of a carrier film and a resin film formed on one surface of the carrier film and obtained by using the resin composition of the present invention. Moreover, since the adhesive sheet of the present invention has a resin film formed by using the resin composition of the present invention, by using this adhesive sheet, a laminate excellent in adhesion of the resin film to a metal (especially copper foil) and low in dielectric loss tangent can be appropriately obtained. Specifically, by using the resin layer obtained by removing the carrier film from the adhesive sheet of the present invention as an adhesive layer (agent) such as a metal foil, a laminate with good adhesion (bonding) between the metal foil, prepreg and resin film and low in dielectric loss tangent can be obtained.

[0155] In addition, the preferred properties of the resin film constituting the adhesive sheet of the present invention are the same as those described in the "resin film" item.

[0156] The adhesive sheet of the present invention can be manufactured by coating the resin composition of the present invention on a carrier film so as to have a predetermined thickness, and then optionally removing the solvent by heating and drying. The coating method is not particularly limited, and any coating device such as a die coater or a bar coater can be used for coating. Here, the carrier film is not particularly limited, and various base materials described in the "resin film" item can be used. In addition, a release agent can be applied to the coating surface of the carrier film to make it easy to remove the carrier film from the resin film.

[0157] (Laminate)

[0158] The laminate of the present invention is a so-called copper-clad laminate, and has a copper foil, and the resin film and / or prepreg of the present invention described above. Specifically, the laminate of the present invention has one or more resin films and / or one or more prepregs, and a copper foil laminated on at least one surface of the resin film and / or prepreg, and at least one of the resin films is composed of the resin film of the present invention and / or at least one of the prepregs is composed of the prepreg of the present invention. Since the laminate of the present invention has the resin film and / or prepreg of the present invention described above, it has excellent adhesion of the resin film and / or prepreg to the copper foil and low dielectric loss tangent. Therefore, the laminate of the present invention is not limited and can preferably be used as a material for manufacturing the printed circuit board of the present invention. In addition, the laminate of the present invention may have any other layers other than the above.

[0159] As the resin film other than the resin film of the present invention, there is no particular limitation, and examples thereof include resin films composed of insulating resins such as polyimide, epoxy resin, and phenolic resin.

[0160] In addition, as the prepreg other than the prepreg of the present invention, there is no particular limitation, and examples thereof include prepregs composed of insulating resins such as polyimide, epoxy resin, and phenolic resin and fiber base materials. As the fiber base material, those described in the "prepreg" item can be used.

[0161] Here, as the material of the copper foil, there is no particular limitation, and copper or a copper alloy can be used. In addition, the copper foil can be either an electrolytic copper foil or a rolled copper foil. The thickness of the copper foil is not particularly limited and can be set to about 3 μm or more and 35 μm or less. Furthermore, from the viewpoint of improving the adhesion to the resin film, the surface of the copper foil can be subjected to surface roughening, silane coupling agent treatment, or rust inhibitor treatment.

[0162] The number (number of sheets) of the copper foil, resin film, and prepreg in the laminate is not particularly limited and can be appropriately set according to the use.

[0163] The laminate of the present invention is not particularly limited and can be produced, for example, by laminating the resin film and / or prepreg of the present invention with a copper foil under heating and pressure. The heating conditions are not particularly limited, the temperature can be set to 150°C or more and 250°C or less, and the heating time can be set to 0.5 hours or more and 10 hours or less. In addition, the pressure is not particularly limited and can be set to 0.5 MPa or more and 5 MPa or less.

[0164] In addition, when the resin film of the present invention is formed on at least one surface of a copper foil as a substrate (that is, when a substrate (copper foil) - resin film is produced), it can be directly used as a laminate, or multiple sheets of this laminate can be laminated, and the obtained laminate can be heated and pressurized as described above to obtain a laminate.

[0165] (Printed Circuit Board)

[0166] The printed circuit board of the present invention is a printed circuit board formed using the above - described laminate of the present invention. Specifically, the printed circuit board of the present invention is formed by forming a circuit pattern on the copper foil surface of the above - described laminate of the present invention. Here, the method of forming a circuit pattern on the copper foil surface of the laminate is not particularly limited, and subtractive method and semi - additive method can be cited. As the semi - additive method, a method of forming a pattern with a resist film on the copper foil surface of the laminate, then plating copper, removing the resist, and etching with an alkaline solution can be cited. The thickness and line width / line pitch ratio of the circuit pattern in the printed circuit board are not particularly limited.

[0167] In addition, the printed circuit board of the present invention can be configured in the form of a multilayer printed circuit board, and the above - described multilayer printed circuit board is formed by using one printed circuit board of the present invention as a core part and laminating one or more identical printed circuit boards of the present invention and / or other known printed circuit boards on at least one of its surfaces. The number of printed circuit boards laminated in the multilayer printed circuit board is not particularly limited.

[0168] The printed circuit board of the present invention is formed using the laminate of the present invention described above, and thus has excellent adhesion to copper foil and a low dielectric loss tangent. Therefore, the printed circuit board of the present invention can preferably be used as, for example, a high-frequency printed circuit board.

[0169] [Examples]

[0170] Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. In the following description, unless otherwise specified, "%" and "parts" representing amounts are based on mass.

[0171] In the examples and comparative examples, the weight-average molecular weight and molecular weight distribution of the polymer, and the adhesion of the resin film to the copper foil and the dielectric loss tangent were measured or evaluated using the following methods, respectively.

[0172] <Weight-average molecular weight and molecular weight distribution>

[0173] For the polymers obtained in each of the examples and each of the comparative examples, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) were measured by gel permeation chromatography, and the molecular weight distribution (Mw / Mn) was calculated.

[0174] Specifically, using a gel permeation chromatograph (manufactured by Tosoh Corporation, "HLC-8220"), and using tetrahydrofuran or cyclohexane as the eluent, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymer were determined as standard polystyrene conversion values. Then, the molecular weight distribution (Mw / Mn) was calculated.

[0175] <Adhesion to copper foil>

[0176] Using a coater (manufactured by TESTER Sangyo Co., Ltd., "PI-1210"), the resin compositions prepared in each example and each comparative example were coated on a copper foil (low-roughened copper foil; 3EC-M2S-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd.) to form a coating film with a film thickness of 50 μm. The coating film was dried at 90°C for 3 minutes to form a resin film. Thereafter, the copper foil with the resin film was cut into two pieces of 10 cm square, the resin films were bonded to each other, and using a vacuum hot press (electric vacuum hot press IMC-182F type manufactured by Imoto Seisakusho), it was heated at a temperature of 200°C and a pressure of 3 Mpa for 1 hour to obtain a copper foil with a resin film having a thickness of 10 μm. The obtained resin-coated copper foil was bonded to a CZ-treated (surface roughening treatment) substrate (679-FG manufactured by Showa Denko, thickness 100 μm) using an adhesive (Aronalpha EXTRAR 2000 manufactured by Toagosei Co., Ltd.) to obtain a laminate having a layer structure of copper foil / resin film / copper foil / adhesive / substrate from top to bottom. Next, a long strip-shaped cut with a width of 10 mm and a length of 100 mm was cut out to the second copper foil of the laminate, and one end in the length direction of the first copper foil was peeled off to prepare a test piece with a tape 70 mm long attached thereto. By performing a tensile test on the test piece, the adhesion strength of the resin film to the copper foil was measured. Specifically, using a tensile testing machine (manufactured by Shimadzu Corporation, "AGS-10kNX"), a 90-degree peel test was performed at 23°C at a tensile speed of 50 mm / minute to measure the adhesion strength of the resin film to the copper foil. The greater the value of the adhesion strength of the resin film to the copper foil, the more excellent the adhesion (copper foil adhesion) of the resin film to the copper foil.

[0177] A: Adhesion strength is 8.0 N / cm or more

[0178] B: Adhesion strength is 7.0 N / cm or more and less than 8.0 N / cm

[0179] C: Adhesion strength is less than 7.0 N / cm

[0180] <Dielectric loss tangent>

[0181] Using a sputtering device (manufactured by Shibaura Machine Co., Ltd., "i-Miller CFS-4EP-LL"), the resin compositions prepared in each example and each comparative example were spin-coated on a 4-inch silicon wafer on which an aluminum film with a film thickness of 50 nm was formed. Then, it was pre-baked on a hot plate at 90 °C for two minutes to form a resin film formed from the resin composition. Next, it was heated in nitrogen at 200 °C for 1 hour to cure the resin film, obtaining a silicon wafer with a 10-μm-thick resin film. The obtained silicon wafer with the resin film was immersed in a 0.1 mol% hydrochloric acid aqueous solution for 12 hours for aluminum etching, thereby peeling the resin film from the silicon wafer. After drying in an oven at 110 °C for 1 hour, it was cut into strips with a width of 2 mm and a length of 50 mm to make test pieces, and the dielectric loss tangent at 10 GHz of the test pieces was measured using a cavity resonator method. According to the following criteria, the dielectric loss tangent of the resin film was evaluated.

[0182] A: Dielectric loss tangent is less than 0.002

[0183] B: Dielectric loss tangent is 0.002 or more and less than 0.004

[0184] C: Dielectric loss tangent is 0.004 or more

[0185] <Prepreg adhesion>

[0186] Using a coater (manufactured by TESTER Sangyo Co., Ltd., "PI-1210"), the resin compositions prepared in each example and each comparative example were coated on a copper foil after CZ treatment to form a coating film with a film thickness of 50 μm. The coating film was dried at 90 °C for 3 minutes to form a resin film. Then, the copper foil with the resin film was cut into squares with a side length of 10 cm, and a prepreg (R-5680(N) manufactured by Matsushita Electric Works, Ltd.), a substrate (679-FG manufactured by Showa Denko, thickness 100 μm) after CZ treatment (surface roughening treatment) were laminated in this order, and they were heated using a vacuum hot press (electric vacuum hot press IMC-182F type manufactured by Imoto Seisakusho) at a temperature of 200 °C and a pressure of 3 Mpa for 1 hour, thereby obtaining a laminate with a layer structure of copper foil / resin film / prepreg / substrate from top to bottom. Then, a long strip-shaped cut with a width of 10 mm and a length of 100 mm was made in the copper foil of the laminate, and one end in the length direction of the copper foil was peeled off to make a test piece with a 70-mm-long tape attached thereto. By performing a tensile test on the test piece, the adhesion strength of the resin film to the prepreg was measured. Specifically, using a tensile testing machine (manufactured by Shimadzu Corporation, "AGS-10kNX"), a 90-degree peeling test was performed at 23 °C at a tensile speed of 50 mm / minute to measure the adhesion strength of the resin film to the prepreg. The greater the value of the adhesion strength of the resin film to the prepreg, the more excellent the adhesion of the resin film to the prepreg (prepreg adhesion).

[0187] A: The sealing strength is 8.0 N / cm or more

[0188] B: The sealing strength is 7.0 N / cm or more and less than 8.0 N / cm

[0189] C: The sealing strength is less than 7.0 N / cm

[0190] (Example 1)

[0191] <Production of Polymer A-1>

[0192] <<Ring-opening polymerization step>>

[0193] 100 parts of methano-tetrahydrofluorene (hereinafter abbreviated as "MTF") as a norbornene monomer, 1.34 parts of allyltrimethoxysilane as a chain transfer agent, 0.186 parts of benzylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene] dichloro(tricyclohexylphosphine) ruthenium as a ring-opening polymerization catalyst, and 300 parts of anisole as a solvent were charged into a glass pressure reactor purged with nitrogen, and reacted at 50°C for 4 hours with stirring to obtain a polymerization reaction solution.

[0194] <<Hydrogenation step>>

[0195] The obtained polymerization reaction solution was charged into an autoclave, and hydrogenation reaction was carried out at 130°C and a hydrogen pressure of 10 MPa with stirring for 5 hours. Thereafter, 900 parts of tetrahydrofuran as a solvent was added to the reaction solution. It was dropped into 8000 parts of methanol, and the formed precipitate was recovered by filtration and dried under reduced pressure at 50°C to obtain a ring-opening polymer hydrogenated product as Polymer A-1. The weight average molecular weight of Polymer A-1 was 41000, and the molecular weight distribution was 2.6.

[0196] By 29 Si-NMR measurement, it was confirmed that a silicon atom was introduced into Polymer A-1. In addition, by 1 H-NMR measurement, when the proportion of the structural unit derived from MTF represented by the following formula (I-1) was set to 100 mol%, the proportion of the structure derived from allyltrimethoxysilane represented by the following formula (II-1) was 1.5 mol%. This indicates that 1.5% of the terminal groups in all the terminal groups of the structural unit represented by the formula (I-1) were replaced by the structure represented by the formula (II-1).

[0197] [Chemical formula 7]

[0198]

[0199] <Preparation of resin composition>

[0200] Mix polymer A-1, triallyl isocyanurate (manufactured by Shinryo Corporation, TAIC), which is a crosslinking agent and an unsaturated bond-containing compound, and dicumyl peroxide (manufactured by Nacalai Tesque, Inc.), which is a peroxide, in the mixing ratio shown in Table 1, and mix anisole (solvent) in an addition amount such that the total of each component other than the solvent becomes 30% by mass, and dissolve each component in the solvent. Next, KP-341 (manufactured by Shin-Etsu Silicone Co., Ltd.), which is a silicone-based surfactant, is added so as to be 0.03% by mass relative to the total mass of the resin composition, and then filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm to prepare a resin composition.

[0201] Then, using the obtained resin composition, various evaluations are carried out as described above. The results are shown in Table 1.

[0202] (Example 2)

[0203] <Manufacture of Polymer A-2>

[0204] In the manufacture of polymer A-1 in Example 1, 1.68 parts of allyl triethoxysilane is used as a chain transfer agent instead of 1.34 parts of allyl trimethoxysilane, and otherwise, it is carried out in the same manner as in Example 1 to obtain a ring-opening polymer hydride of polymer A-2. The weight-average molecular weight of polymer A-2 is 43,500, and the molecular weight distribution is 2.8.

[0205] By 29 Si-NMR measurement, it was confirmed that a silicon atom was introduced into polymer A-2. In addition, by 1 H-NMR measurement, it was confirmed that when the proportion of the structural unit derived from MTF represented by the following formula (I-2) was set to 100 mol%, the proportion of the structure derived from allyl triethoxysilane represented by the following formula (II-2) was 1.5 mol%.

[0206] [Chemical formula 8]

[0207]

[0208] <Preparation of Resin Composition>

[0209] Using polymer A-2, otherwise, it is carried out in the same manner as in Example 1 to prepare a resin composition. Then, using the obtained resin composition, various evaluations are carried out as described above. The results are shown in Table 1.

[0210] (Example 3)

[0211] <Manufacture of Polymer A-3>

[0212] In the production of the polymer of Example 1, 1.91 parts of trimethoxy(7-octen-1-yl)silane was used as a chain transfer agent instead of 1.34 parts of allyltrimethoxysilane, and otherwise, the procedure was the same as in Example 1 to obtain a ring-opening polymer hydride as Polymer A-3. The weight-average molecular weight of Polymer A-3 was 40,300, and the molecular weight distribution was 2.9.

[0213] By 29 Si-NMR measurement, it was confirmed that a silicon atom was introduced into Polymer A-3. Further, by 1 H-NMR measurement, when the proportion of the structural unit derived from MTF represented by the following formula (I-3) was set to 100 mol%, the proportion of the structure derived from trimethoxy(7-octen-1-yl)silane represented by the following formula (II-3) was confirmed to be 1.5 mol%.

[0214] [Chemical formula 9]

[0215]

[0216] <Preparation of resin composition>

[0217] Using Polymer A-3, otherwise, the procedure was the same as in Example 1 to prepare a resin composition. Then, using the obtained resin composition, various evaluations were carried out as described above. The results are shown in Table 1.

[0218] (Example 4)

[0219] In the preparation of the resin composition, allyl isocyanurate derivative (manufactured by Shikoku Kasei Kogyo Co., Ltd., L-DAIC) was used as a crosslinking agent instead of triallyl isocyanurate (manufactured by Shinryo Corporation, TAIC), and otherwise, the procedure was the same as in Example 3 to prepare a resin composition. Then, using the obtained resin composition, various evaluations were carried out as described above. The results are shown in Table 1.

[0220] (Example 5)

[0221] <Production of Polymer A-4>

[0222] In the production of Polymer A-1 of Example 1, the amount of MTF as a norbornene monomer was changed from 100 parts to 78 parts, 22 parts of ethylidene norbornene (hereinafter abbreviated as "ENB") as a norbornene monomer was added, and 2.13 parts of trimethoxy(7-octen-1-yl)silane was added as a chain transfer agent in place of 1.34 parts of allyltrimethoxysilane. The amount of benzylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichlororuthenium(tricyclohexylphosphine) as a ring-opening polymerization catalyst was changed from 0.186 parts to 0.208 parts. Otherwise, the procedure was the same as in Example 1, and a hydrogenated ring-opening polymer as Polymer A-4 was obtained. The weight-average molecular weight of Polymer A-4 was 35,500, and the molecular weight distribution was 2.7.

[0223] By 29 Si-NMR measurement, it was confirmed that a silicon atom was introduced into Polymer A-4. Further, by 1 H-NMR measurement, when the total proportion of the structural units derived from MTF and the structural units derived from ENB was set to 100 mol%, the proportion of the structural units derived from MTF represented by the following formula (I-4a) was 70 mol%, the proportion of the structural units derived from ENB represented by the following formula (I-4b) was 30 mol%, and the proportion of the structure derived from trimethoxy(7-octen-1-yl)silane represented by the following formula (II-4) was 1.5 mol%.

[0224] [Chemical formula 10]

[0225]

[0226] <Preparation of resin composition>

[0227] Using Polymer A-4, otherwise, the procedure was the same as in Example 1, and a resin composition was prepared. Then, using the obtained resin composition, various evaluations were carried out as described above. The results are shown in Table 1. In addition, the prepreg adhesion evaluation was not performed in Example 5.

[0228] (Example 6)

[0229] <Production of Polymer A-5>

[0230] In the production of the polymer of Example 1, 100 parts of MTF as a norbornene monomer was changed to 100 parts of ethylidene tetracyclododecene (hereinafter abbreviated as "ETD"), and as a chain transfer agent, 1.87 parts of trimethoxy(7-octen-1-yl)silane was added instead of 1.34 parts of allyltrimethoxysilane. The amount of benzylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichlororuthenium(tricyclohexylphosphine) as a ring-opening polymerization catalyst was changed from 0.186 parts to 0.182 parts. Except for this, the procedure was the same as in Example 1, and a ring-opening polymer hydrogenated product as Polymer A-5 was obtained. The weight-average molecular weight of Polymer A-5 was 42,000, and the molecular weight distribution was 2.9.

[0231] By 29 Si-NMR measurement, it was confirmed that a silicon atom was introduced into Polymer A-5. In addition, by 1 H-NMR measurement, it was confirmed that when the proportion of the structural unit derived from ETD represented by the following formula (I-5) was set to 100 mol%, the proportion of the structure derived from trimethoxy(7-octen-1-yl)silane represented by the following formula (II-5) was 1.5 mol%.

[0232] [Chemical formula 11]

[0233]

[0234] <Preparation of resin composition>

[0235] Using Polymer A-5, except for this, the procedure was the same as in Example 1, and a resin composition was prepared.

[0236] Then, using the obtained resin composition, various evaluations were carried out as described above. The results are shown in Table 1. In addition, the evaluation of the prepreg adhesion was not carried out in Example 6.

[0237] (Example 7)

[0238] In the preparation of the resin composition, the amount of dicumyl peroxide as a crosslinking agent was changed from 1 part by mass to 5 parts by mass, and the procedure was the same as in Example 3 to prepare a resin composition. Then, using the obtained resin composition, various evaluations were carried out as described above. The results are shown in Table 1.

[0239] (Example 8)

[0240] In the preparation of the resin composition, the amount of dicumyl peroxide as a crosslinking agent was changed from 1 part by mass to 8 parts by mass, and except for this, the procedure was the same as in Example 3 to prepare a resin composition. Then, using the obtained resin composition, various evaluations were carried out as described above. The results are shown in Table 1.

[0241] (Example 9)

[0242] <Manufacture of Polymer A-6>

[0243] In the manufacture of Polymer A-1 in Example 1, the amount of MTF as a norbornene monomer was changed from 100 parts to 87.1 parts, 12.8 parts of 1,5-cyclooctadiene (hereinafter abbreviated as "COD") as a non-norbornene monomer was added, 2.08 parts of trimethoxy(7-octen-1-yl)silane was added to replace 1.34 parts of allyltrimethoxysilane as a chain transfer agent, and the amount of benzylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichlororuthenium(tricyclohexylphosphine) as a ring-opening polymerization catalyst was changed from 0.186 parts to 0.175 parts. Otherwise, the procedure was the same as in Example 1, and a ring-opening polymer hydrogenated product as Polymer A-6 was obtained. The weight-average molecular weight of Polymer A-6 was 21,000, and the molecular weight distribution was 1.7.

[0244] By 29 Si-NMR measurement, it was confirmed that a silicon atom was introduced into Polymer A-6. In addition, by 1 H-NMR measurement, when the total proportion of the structural units derived from MTF and the structural units derived from COD was set to 100 mol%, the proportion of the structural units derived from MTF represented by the following formula (I-6a) was 80 mol%, the proportion of the structural units derived from COD represented by the following formula (I-6b) was 20 mol%, and the proportion of the structure derived from trimethoxy(7-octen-1-yl)silane represented by the following formula (II-6) was 1.5 mol%.

[0245] [Chemical formula 12]

[0246]

[0247] <Preparation of Resin Composition>

[0248] Using Polymer A-6, otherwise, the procedure was the same as in Example 1, and a resin composition was prepared. Then, using the obtained resin composition, various evaluations were carried out as described above. The results are shown in Table 2.

[0249] (Example 10)

[0250] <Manufacture of Polymer A-7>

[0251] In the production of Polymer A-1 of Example 1, the amount of MTF as a norbornene monomer was changed from 100 parts to 93.8 parts, 6.2 parts of COD was added, 2.08 parts of trimethoxy(7-octen-1-yl)silane was added to replace 1.34 parts of allyltrimethoxysilane as a chain transfer agent, and the amount of benzylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichlororuthenium(tricyclohexylphosphine) as a ring-opening polymerization catalyst was changed from 0.186 parts to 0.168 parts. Otherwise, the procedure was the same as in Example 1 to obtain a hydrogenated ring-opening polymer as Polymer A-7. The weight-average molecular weight of Polymer A-7 was 22,000, and the molecular weight distribution was 1.7.

[0252] By 29 Si-NMR measurement, it was confirmed that a silicon atom was introduced into Polymer A-7. Further, by 1 H-NMR measurement, when the total proportion of the structural units derived from MTF and the structural units derived from COD was set to 100 mol%, the proportion of the structural units derived from MTF represented by the following formula (I-7a) was 90 mol%, the proportion of the structural units derived from COD represented by the following formula (I-7b) was 10 mol%, and the proportion of the structure derived from trimethoxy(7-octen-1-yl)silane represented by the following formula (II-7) was 1.5 mol%.

[0253] [Chemical formula 13]

[0254]

[0255] <Preparation of resin composition>

[0256] Using Polymer A-7, otherwise, the procedure was the same as in Example 1 to prepare a resin composition. Then, using the obtained resin composition, various evaluations were carried out as described above. The results are shown in Table 2.

[0257] (Example 11)

[0258] <Production of Polymer A-8>

[0259] In the production of the polymer of Example 1, 0.96 parts of trimethoxy(7-octen-1-yl)silane was used as a chain transfer agent to replace 1.34 parts of allyltrimethoxysilane. Otherwise, the procedure was the same as in Example 1 to obtain a hydrogenated ring-opening polymer as Polymer A-8. The weight-average molecular weight of Polymer A-8 was 68,000, and the molecular weight distribution was 2.9.

[0260] By 29 Si-NMR measurement, it was confirmed that a silicon atom was introduced into Polymer A-8. Further, by 1By \(^1\)H-NMR measurement, it was confirmed that when the proportion of the structural unit derived from MTF represented by the following formula (I-8) was set to 100 mol%, the proportion of the structure derived from trimethoxy(7-octen-1-yl)silane represented by the following formula (II-8) was 0.75 mol%.

[0261] [Chemical formula 14]

[0262]

[0263] <Preparation of resin composition>

[0264] Using polymer A-8, otherwise, carried out in the same manner as in Example 1 to prepare a resin composition. Then, using the obtained resin composition, various evaluations were carried out as described above. The results are shown in Table 2.

[0265] (Examples 12 to 14)

[0266] <Preparation of resin composition>

[0267] The composition of the resin composition was as shown in Table 2. Otherwise, carried out in the same manner as in Example 1 to prepare a resin composition. Then, using the obtained resin composition, various evaluations were carried out as described above. The results are shown in Table 2.

[0268] (Comparative Example 1)

[0269] <Manufacture of polymer B-1>

[0270] In the manufacture of polymer A-1 in Example 1, 0.69 part of 1-hexene was used as a chain transfer agent instead of 1.34 parts of allyltrimethoxysilane. Otherwise, carried out in the same manner as in Example 1 to obtain a ring-opening polymer hydrogenated product as polymer B-1. The weight-average molecular weight of the ring-opening polymer B-1 was 32,000, and the molecular weight distribution was 1.9. By 29 \(^{29}\)Si-NMR measurement, it was confirmed that no silicon atom was introduced into polymer B-1. In addition, by 1 \(^1\)H-NMR measurement, it was confirmed that the proportion of the structural unit derived from MTF represented by the following formula (I-9) was 100 mol%.

[0271] [Chemical formula 15]

[0272]

[0273] <Preparation of resin composition>

[0274] Carried out in the same manner as in Example 1 to prepare a resin composition. Then, using the obtained resin composition, various evaluations were carried out as described above. The results are shown in Table 2.

[0275] (Comparative Example 2)

[0276] <Manufacture of Polymer B-2>

[0277] In the manufacture of Polymer A-1 in Example 1, the amount of MTF as a norbornene monomer was changed from 100 parts to 93.1 parts, 6.9 parts of 5-(triethoxysilyl)-2-norbornene (hereinafter abbreviated as "NBSi") as a norbornene monomer having a silyl group as a substituent was added, 0.69 part of 1-hexene was added instead of 1.34 parts of allyltrimethoxysilane as a chain transfer agent, and the amount of benzylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichlororuthenium(tricyclohexylphosphine) as a polymerization initiation catalyst was changed from 0.186 part to 0.183 part. Otherwise, the procedure was the same as in Example 1, and a ring-opening polymer hydride as Polymer B-2 was obtained. The weight-average molecular weight of Polymer B-2 was 33,500, and the molecular weight distribution was 2.3. By 29 Si-NMR measurement, it was confirmed that a silicon atom was introduced into Polymer B-2. In addition, by 1 H-NMR measurement, when the total proportion of the structural unit derived from MTF and the structural unit derived from NBSi was set to 100 mol%, the proportion of the structural unit derived from MTF represented by the following formula (I-10a) was 95 mol%, and the proportion of the structural unit derived from NBSi represented by the following formula (I-10b) was 5 mol%.

[0278] [Chemical Formula 16]

[0279]

[0280] <Preparation of Resin Composition>

[0281] Using Polymer B-2, otherwise, the procedure was the same as in Example 1 to prepare a resin composition. Then, using the obtained resin composition, various evaluations were carried out as described above. The results are shown in Table 2.

[0282] [Table 1]

[0283]

[0284] [Table 2]

[0285]

[0286] From the results of Tables 1 and 2, it can be seen that the resin films of Examples 1 to 14 using a specified polymer having a specified silyl group at at least one end of the main chain have excellent adhesion to copper foil and a low dielectric loss tangent. In contrast, it can be seen that the resin film of Comparative Example 1 using a specified polymer not having a specified silyl group at the end of the main chain has poor adhesion to copper foil. In addition, the resin film of Comparative Example 2 using a specified polymer having a specified silyl group only in the side chain of the main chain has poor adhesion to copper foil and a high dielectric loss tangent.

[0287] Industrial applicability

[0288] According to the present invention, there can be provided a resin composition capable of forming a resin film having excellent adhesion to a metal (particularly copper foil) and a low dielectric loss tangent, a resin film formed using the resin composition, a prepreg and a bonding sheet, a laminate having the resin film or the prepreg, and a printed circuit board formed using the laminate. Further, according to the present invention, an object is to provide a polymer capable of providing the above resin composition.

Claims

1. A polymer comprising a structural unit represented by the following formula (I), at least one end of the polymer having a structure represented by the following formula (II), In formula (I), R1 to R4 each independently represent a hydrogen atom, an alkyl group having 1 or more and 10 or less carbon atoms, or an aryl group having 6 or more and 30 or less carbon atoms, m represents an integer of 0 to 3, and R1 to R4 can bond to form a ring, In formula (II), each R5 independently represents a linear or branched alkyl group having 1 or more and 10 or less carbon atoms, or an alkoxy group having 1 or more and 10 or less carbon atoms, and n represents an integer of 1 to 30.

2. A resin composition comprising the polymer according to claim 1.

3. The resin composition according to claim 2, wherein, The resin composition further comprises a crosslinking agent.

4. The resin composition according to claim 3, wherein, The crosslinking agent comprises a compound having an unsaturated bond.

5. The resin composition according to claim 3, wherein, The crosslinking agent comprises a peroxide.

6. A resin film formed using the resin composition according to any one of claims 2 to 5.

7. A prepreg composed of a fiber substrate and the resin composition according to any one of claims 2 to 5.

8. An adhesive sheet composed of a carrier film and a resin film formed on one surface of the carrier film, the resin film being obtained using the resin composition according to any one of claims 2 to 5.

9. A laminate having a copper foil and the resin film according to claim 6.

10. A printed circuit board formed using the laminate according to claim 9.

11. A laminate having a copper foil and the prepreg according to claim 7.

12. A printed circuit board formed using the laminate according to claim 11.

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