Polymer, method for producing same, resin composition, and electronic component

Abstract

This polymer is characterized by comprising a structural unit (I) represented by formula (I) and a structural unit (II) represented by formula (II). In formula (I), two of R1-R4 together may form a ring structure; the R1-R4 that do not form a ring structure each independently are a hydrogen atom, an alkyl group, an aromatic ring group, or a radical crosslinkable group; alkyl groups and aromatic ring groups may have a hydroxyl group as a substituent; and m is an integer ranging of

Description

[Technical Field]

[0001] This invention relates to polymers and their manufacturing methods, resin compositions, and electronic components. [Previous Technology]

[0002] In the past, various resin films have been provided on electronic components such as integrated circuit elements or organic EL elements in the form of protective films to prevent the deterioration or damage of the components themselves, planarization films to planarize the surface of the components or wiring, electrical insulation films to maintain electrical insulation, pixel separation films to separate the light-emitting parts, and optical films to concentrate and diffuse light.

[0003] Conventionally, polymers obtained by ring-opening polymerization of norethene monomers have been used as resin materials constituting such resin films (see, for example, Patent Documents 1 to 3).

[0004] 『Patent Documents』 《Patent Document 1》: Japanese Patent Publication No. 2006-156821 《Patent Document 2》: Japanese Patent Publication No. 2009-167433 《Patent Document 3》: Japanese Patent Publication No. 2018-172558 [Summary of the Invention]

[0005] Therefore, for resin films used in the various applications described above, excellent heat resistance and strength and a low coefficient of linear expansion are required.

[0006] Therefore, the object of the present invention is to provide a polymer capable of preparing a resin composition, said resin composition being able to form a resin film with excellent heat resistance and strength and a low coefficient of linear expansion.

[0007] Furthermore, the object of the present invention is to provide a resin composition capable of forming a resin film with excellent heat resistance and strength and a low coefficient of linear expansion.

[0008] Furthermore, the object of the present invention is to provide an electronic component having the resin film.

[0009] The inventors have devoted themselves to research in order to achieve the above-mentioned objective. Then, the inventors discovered that if a polymer containing two specified structural units is used, a resin composition that forms a resin film with excellent heat resistance and strength and a low coefficient of linear expansion can be prepared, thereby completing the present invention.

[0010] That is, this invention aims to solve the above-mentioned problems. The present invention is [1] a polymer that includes a structural unit (I) shown by the following formula (I) and a structural unit (II) shown by the following formula (II). 『Chemical 1』・・・(I) In formula (I), R1 to R4 can also form a ring structure together. R1 to R4 that do not form a ring structure are independently hydrogen atoms, alkyl groups, aromatic ring groups or free radical crosslinking groups. Alkyl groups and aromatic ring groups can also have hydroxyl groups as substituents. m is an integer of 0 or more and 4 or less. 『Chemical 2』・・・(II) In formula (II), X is a divalent organic group, Y is a tetravalent organic group, Z is a divalent organic group, and n is an integer of 0 or more.

[0011] If a polymer containing the two structural units specified above is used, a resin composition that forms a resin film with excellent heat resistance and strength and a low coefficient of linear expansion can be prepared.

[0012] [2] In the polymer described above [1], it is preferable that at least one of the aforementioned R1 to R4 is a free radical crosslinking group.

[0013] If at least one of R1 to R4 is a polymer of free radical crosslinking group, it can be used in a photosensitive resin composition where the solubility of the exposed part in the developer decreases and the exposed part will be left with a negative shape due to development.

[0014] [3] In the polymers of [1] or [2] above, for example, the aforementioned X is a divalent organic group represented by any of the following formulas (Xa) to (Xc). In formulas (Xa) to (Xc), R5 is an alkyl group, R6 is an alkyl group or an aromatic group, and p is an integer of 0 or more and 10 or less.

[0015] [4] In any of the polymers [1] to [3] above, for example, the aforementioned Y is a tetravalent organic group represented by any of the following formulas (Ya) to (Yf). In formulas (Ya) to (Yf) of "Chemical 4", R7, R8, R15 and R16 are independently hydrogen atoms, halogen atoms, alkyl or aromatic ring groups, respectively. R9 and R10 can also form a ring structure together. R9 and R10 that do not form a ring structure are independently hydrogen atoms, halogen atoms, alkyl or aromatic ring groups, respectively. R11 and R14 are independently oxygen atoms, sulfur atoms or carbonyl groups, respectively. R12 and R13 can also form a ring structure together. R12 and R13 that do not form a ring structure are independently hydrogen atoms, halogen atoms, alkyl or aromatic ring groups, respectively. Alkyl and aromatic ring groups can also have halogen atoms as substituents. q and r are independently integers of 0 or more and less than 3. s and t are independently integers of 0 or more and less than 4.

[0016] [5] In any of the polymers [1] to [4] above, for example, the aforementioned Z is a divalent organic group represented by any of the following formulas (Za) to (Zf). In formulas (Za) to (Zf) of "Chemical 5", R17, R18, R24 and R25 are independently hydrogen atoms, halogen atoms, alkyl or aromatic ring groups, respectively; R19 and R26 are independently oxygen atoms, sulfur atoms or carbonyl groups, respectively; R20 and R21 can also form a ring structure together; R20 and R21 that do not form a ring structure are independently hydrogen atoms, halogen atoms, alkyl or aromatic ring groups, respectively; R22 and R23 can also form a ring structure together; R22 and R23 that do not form a ring structure are independently hydrogen atoms, halogen atoms, alkyl or aromatic ring groups, respectively; alkyl and aromatic ring groups can also have halogen atoms as substituents; u, v, w and x are independently integers greater than 0 and less than 4.

[0017] [6] In any of the polymers [1] to [5] above, it is preferable that the concentration of amide groups in the aforementioned structural unit (II) is 13% by mass or more and 20% by mass or less.

[0018] If the concentration of amide groups in structural unit (II) is within the range specified above, the strength of the resin film formed from the resin composition containing the polymer can be further improved while the dielectric loss tangent of the resin film is reduced.

[0019] Furthermore, in this invention, the amide concentration in structural unit (II) refers to the average mass ratio of the amide portion in each structural unit (II) contained in the polymer. Moreover, the amide concentration in structural unit (II) can be measured using nuclear magnetic resonance (NMR) methods such as 1H-NMR or 13C-NMR. Furthermore, the amide concentration in structural unit (II) is generally defined to be consistent with the amide concentration in the polyamide compound forming the structural unit (II), i.e., the polyamide compound used in the manufacture of the polymer.

[0020] Furthermore, this invention is intended to solve the above-mentioned problems. The present invention is [7] a resin composition comprising any of the polymers [1] to [6] mentioned above.

[0021] If it is a resin composition contained in the polymer described above, a resin film with excellent heat resistance and strength and a low coefficient of linear expansion can be formed.

[0022] [8] The resin composition of [7] above preferably contains more free radical initiators.

[0023] In addition to polymers containing free radical crosslinking groups, resin compositions also contain free radical initiators, which can be used as photosensitive resin compositions where the solubility of the exposure area in the developer decreases and the exposure area will be left with a negative shape due to development.

[0024] [9] The resin composition of [7] or [8] above preferably contains at least one of a ketone solvent and an ether solvent.

[0025] If at least one of ketone-based solvents and ether-based solvents is used as the solvent, the polymer can be well dissolved, thereby improving the coatability of the resin composition and the uniformity of the formed resin film.

[0026]

[10] In the resin composition of [9] above, preferably the ketone solvent contains at least one of cyclopentanone and cyclohexanone, and the ether solvent contains at least one of the group consisting of tetrahydrofuran, tetrahydropiperanone, methyltetrahydropiperanone and methoxybenzene.

[0027] If at least one of the ketone-based solvents and ether-based solvents specified above is used as the solvent, the polymer can be dissolved better, and the coatability of the resin composition and the uniformity of the formed resin film can be further improved.

[0028] Furthermore, this invention aims to smoothly solve the above-mentioned problems. The present invention is

[11] a method for manufacturing a polymer, which includes a step of performing a ring-opening polymerization reaction of a norethene monomer (I′) shown in the following formula (I′) and a polyimide compound (II′) shown in the following formula (II′). 『Chemical 6』・・・(I′) In formula (I′), R1 to R4 can also form a ring structure together. R1 to R4 that do not form a ring structure are independently hydrogen atoms, alkyl groups, or aromatic ring groups. Alkyl groups and aromatic ring groups can also have hydroxyl groups as substituents. m is an integer of 0 or more and 4 or less. 『Chemical 7』・・・(II′) In formula (II′), X is a divalent organic group, Y is a tetravalent organic group, Z is a divalent organic group, and n is an integer of 0 or more.

[0029] According to the polymer manufacturing method of the present invention, a polymer capable of preparing a resin composition can be efficiently manufactured, wherein the resin composition forms a resin film with excellent heat resistance and strength and a low coefficient of linear expansion.

[0030]

[12] In the method for manufacturing the polymer described in

[11] above, it is preferable that the concentration of amide groups in the aforementioned polyamide compound (II′) is 13% by mass or more and 20% by mass or less.

[0031] If the amide group concentration of the polyamide compound (II′) is within the range specified above, the strength of the resin film formed from the resin composition prepared using the manufactured polymer can be further improved while the dielectric loss tangent of the resin film is reduced.

[0032] Furthermore, in this invention, the amide group concentration in the polyimide compound (II′) refers to the average mass percentage of the amide group portion in the polyimide compound (II′) used in the manufacture of the polymer. Moreover, the amide group concentration in the polyimide compound (II′) can be measured using nuclear magnetic resonance (NMR) methods such as 1H-NMR or 13C-NMR. Furthermore, the amide group concentration in the polyimide compound (II′) is generally defined as a value consistent with a calculated value obtained by following the methods described in the examples of this specification, based on the amounts of tetracarboxylic dianhydride, diamine, and end sealant used in the synthesis of the polyimide compound (II′).

[0033] Furthermore, this invention is intended to solve the above-mentioned problems. The present invention is

[13] an electronic component, characterized in that it comprises a resin film formed from any of the resin compositions [6] to

[10] above.

[0034] The electronic component of the present invention is high-performance because it has a resin film with excellent heat resistance and strength and a low coefficient of linear expansion formed by the resin composition described above.

[0035]

[14] The aforementioned resin film of the electronic component in

[13] above can also be patterned.

[0036] According to the present invention, a polymer capable of preparing a resin composition can be provided, the resin composition being able to form a resin film with excellent heat resistance and strength and a low coefficient of linear expansion.

[0037] Furthermore, according to the present invention, a resin composition capable of forming a resin film with excellent heat resistance and strength and a low coefficient of linear expansion can be provided.

[0038] Furthermore, according to the present invention, electronic components having the resin film can be provided.

Implementation Method

[0040] Accordingly, the polymer of the present invention can be used in the preparation of the resin composition of the present invention. Furthermore, the polymer of the present invention can be manufactured using the manufacturing method of the polymer of the present invention.

[0041] Moreover, the resin composition of the present invention is not particularly limited and can be used when forming a resin film that can be used for electronic components such as integrated circuit elements, organic EL elements, and semiconductor packages. In particular, the resin composition of the present invention is suitably used when manufacturing insulating organic films such as organic ELs, semiconductor packages, printed wiring boards, and solder resists. Furthermore, in the case of using a radical initiator and a polymer having a radical crosslinkable group as the polymer of the present invention together, the resin composition of the present invention can be suitably used as a negative photosensitive resin composition in which the solubility of the exposed portion in the developer decreases and the exposed portion remains after development. And, as the active energy ray used when exposing the resin film formed using the resin composition of the present invention, there is no particular limitation, and examples include: light rays of a single wavelength such as ultraviolet rays, g-line, h-line, i-line, light rays such as KrF excimer laser light and ArF excimer laser light, and particle rays such as electron beams.

[0042] Furthermore, the electronic component of the present invention includes a resin film formed using the resin composition of the present invention.

[0043] (Polymer)

[0044] The polymer of the present invention includes a structural unit (I) represented by the following formula (I) and a structural unit (II) represented by the following formula (II).

[0045] 'Chemical formula 8'... (I) In formula (I), two of R1 to R4 may combine to form a ring structure, and R1 to R4 that do not form a ring structure are each independently a hydrogen atom, an alkyl group, an aromatic ring group, or a radical crosslinkable group. The alkyl group and the aromatic ring group may also have a hydroxyl group as a substituent, and m is an integer of 0 or more and 4 or less.

[0046] 'Chemical formula 9'... (II) In formula (II), X is a divalent organic group, Y is a tetravalent organic group, Z is a divalent organic group, and n is an integer of 0 or more.

[0047] Since the polymer of the present invention includes the above-specified structural unit (I) and structural unit (II), it is possible to form a resin film having excellent heat resistance, strength, and a low linear expansion coefficient.

[0048] In addition, the polymer of the present invention may optionally further include a structural unit other than the above-described structural unit (I) and structural unit (II).

[0049] 〈Structural unit (I)〉

[0050] In the structural unit (I) shown in the above formula (I), two of R1 to R4 may also form a ring structure together, and R1 to R4 that do not form a ring structure are independently hydrogen atoms, alkyl groups, aromatic ring groups or free radical crosslinking groups. In addition, the alkyl and aromatic ring groups constituting R1 to R4 may also have hydroxyl groups as substituents. And m is an integer of 0 or more and 4 or less.

[0051] Furthermore, the polymer of the present invention may contain only one structural unit (I) or may contain multiple units.

[0052] Free radical cross-linking radical

[0053] Here, as a free radical crosslinking group that can constitute R1 to R4 without forming a ring structure, it is not particularly limited as long as it has a molecular skeleton that "has carbon-carbon unsaturated bonds (especially vinyl unsaturated bonds) and can carry out free radical reactions based on free radicals generated by free radical initiators". As free radical crosslinking groups, free radical crosslinking groups with styrene skeletons and free radical crosslinking groups with acrylate skeletons are good examples.

[0054] [Free radical crosslinking group with a styrene backbone]

[0055] If the structural unit (I) of the cyclic olefin polymer has a free radical crosslinking group with a styrene backbone, the dielectric loss tangent of the resin film can be reduced, presumably because the proportion of polar atoms in the structural unit (I) will be reduced. Furthermore, for the resin film, the patterning characteristics in the case of using cyclic ketones as a developer can be further improved.

[0056] Here, as a free radical crosslinking group having a styrene skeleton, an example of a group represented by the following formula (III) can be cited.

[0057] 『Transformation 10』・・・(III)

[0058] In formula (III), R 27 and R 29 are each independently a single bond or an alkyl group with 1 or more carbon atoms and less than 10 carbon atoms, R 28 is an oxygen atom or a sulfur atom, R 30 is a hydrogen atom or a substituent, and y is an integer of 0 or more and less than 4.

[0059] In formula (III), the alkyl group having 1 or more and 10 or less carbon atoms as R 27 and R 29 is not particularly limited, but it is preferable to have chain alkyl groups having 1 or more and 6 or less carbon atoms such as methylene, ethyl, propyl, n-butyl, and isobutyl. It is even more preferable to have straight-chain alkyl groups having 1 or more and 6 or less carbon atoms such as methylene, ethyl, propyl, and n-butyl. It is even more preferable to have straight-chain alkyl groups having 1 or more and 3 or less carbon atoms such as methylene, ethyl, and propyl. Methylene is particularly preferred.

[0060] In formula (III), there are no particular restrictions on the substituents that can be used to obtain R 30, and examples include alkyl groups such as methyl and ethyl, and halogen groups such as fluorine and chloro.

[0061] Furthermore, in formula (III), y is preferably 0, that is, the phenyl group (-C6H4-) constituting the styrene skeleton is preferably not substituent.

[0062] [Free radical crosslinking group with acrylate backbone]

[0063] If the structural unit (I) has a free radical crosslinking group with an acrylate backbone, the dielectric loss tangent of the resin film formed from the resin composition containing the polymer can be reduced, while the elongation can be improved. Furthermore, the patterning characteristics of the resin film can be improved when using a cyclic ketone as a developer.

[0064] Here, as a free radical crosslinking group having an acrylate backbone, examples can be given by the group shown in the following formula (IV).

[0065] 『Chemistry 11』・・・(IV)

[0066] In formula (IV), R 31 refers to an alkyl group having 1 or more carbon atoms and less than 10 carbon atoms, and R 32 refers to a hydrogen atom or an alkyl group.

[0067] In the free radical crosslinking group shown in Formula (IV), since the substituted or unsubstituted acrylonitrile is bonded to the cyclic olefin structure through the alkyl group shown in R 31, the mobility of the acrylonitrile is increased. As a result of this increased mobility, the crosslinking reactivity of the acrylonitrile increases. It can be inferred that for this reason, if a polymer "containing a structural unit (I) having a free radical crosslinking group shown in Formula (IV)" is used, the dielectric loss tangent of the resin film formed from the resin composition can be reduced, while the elongation can be improved, and for the resin film, the patterning characteristics in the case of using a cyclic ketone as a developer can be improved.

[0068] In formula (IV), the alkyl group having 1 or more and 10 or less carbon atoms as R 31 is not particularly limited, but it is preferable to be a chain alkyl group having 1 or more and 6 or less carbon atoms such as methylene, ethyl, propyl, n-butyl, and isobutyl, and it is even more preferable to be a straight-chain alkyl group having 1 or more and 6 or less carbon atoms such as methylene, ethyl, propyl, and n-butyl, and it is even more preferable to be a straight-chain alkyl group having 1 or more and 3 or less carbon atoms such as methylene, ethyl, and propyl, and it is particularly preferable to be methylene.

[0069] In formula (IV), the alkyl group that forms R 32 is not particularly limited, and examples include alkyl groups having 1 or more carbon atoms and 5 or fewer carbon atoms. Among them, methyl or ethyl is preferred as the alkyl group that forms R 32.

[0070] Structures other than free radical crosslinking groups

[0071] In formula (I), the alkyl group that is R1 to R4 (unsubstituted) other than the radical crosslinking group is not particularly limited, but examples of alkyl groups having 1 or more carbon atoms and 10 or less can be given, with alkyl groups having 1 or more carbon atoms and 5 or less being preferred, and methyl and ethyl being more preferred.

[0072] In formula (I), the (unsubstituted) aromatic ring group of R1 to R4 other than the free radical crosslinking group is not particularly restricted as long as it does not conform to the free radical crosslinking group. Examples include: phenyl, naphthyl, fumoniyl, anthracene, triphenyl, biphenyl and other aromatic ring groups with 4 or more carbon atoms and less than 30 carbon atoms.

[0073] Furthermore, as described above, in formula (I), the alkyl and aromatic ring groups constituting R1 to R4 may also have hydroxyl groups as substituents.

[0074] Furthermore, the ring structure formed by the combination of two of R1 to R4 other than the free radical crosslinking group is not particularly limited. Examples include: a monocyclic or polycyclic structure containing a carbon ring, with a structure containing an aromatic ring (hereinafter sometimes referred to as "aromatic ring structure") being preferred.

[0075] Furthermore, in formula (I), as mentioned above, m is an integer greater than or equal to 0 and less than or equal to 4, preferably 0, 1 or 2, and more preferably 0 or 1.

[0076] [Suitable structure of structural unit (I)]

[0077] Furthermore, the polymer preferably comprises, for example, the following two as structural units (I): (i) at least one of R1 to R4 in formula (I) is a free radical crosslinking group or a hydroxyalkyl group (i.e., an alkyl group having a hydroxyl group as a substituent) (hereinafter referred to as structural unit (Ia)); and (ii) R1 to R4 in formula (I) are structural units other than free radical crosslinking groups and hydroxyalkyl groups (hereinafter referred to as structural unit (Ib)).

[0078] Herein, in structural unit (Ia), at least one of R1 to R4 is a free radical crosslinking group or a hydroxyalkyl group. R1 to R4 that do not meet either the requirements of a free radical crosslinking group or a hydroxyalkyl group may also form a ring structure together. R1 to R4 that do not meet either the requirements of a free radical crosslinking group or a hydroxyalkyl group and do not form a ring structure are independently hydrogen atoms, alkyl groups (limited to those without a hydroxyl group as a substituent), or aromatic ring groups (which may also have a hydroxyl group as a substituent).

[0079] Moreover, from the viewpoint of improving the patterning characteristics of a resin film formed from a resin composition containing a polymer when using a cyclic ketone as a developer, it is preferable that at least one of R1 to R4 in the structural unit (Ia) is a free radical crosslinking group. From the viewpoint of facilitating the synthesis of the polymer and improving production efficiency, it is preferable that one of R1 to R4 is a free radical crosslinking group and the others are hydrogen atoms.

[0080] Furthermore, in the structural unit (Ia), m is an integer greater than or equal to 0 and less than or equal to 4, preferably 0, 1 or 2, with 0 or 1 being more preferred.

[0081] Furthermore, in the structural unit (Ib), R1 to R4 can be anything other than a free radical crosslinking group and a hydroxyalkyl group. However, from the viewpoint of reducing the dielectric loss tangent of the resin film formed from the resin composition containing the polymer, and at the same time improving the strength of the resin film, it is preferable that at least one of R1 to R4 is an aromatic ring group or that two of R1 to R4 are combined to form an aromatic ring structure. R1 to R4 that do not conform to an aromatic ring group and do not form an aromatic ring structure are each independently a hydrogen atom or an alkyl group (but the alkyl group does not have a hydroxyl group as a substituent). It is more preferable that one of R1 to R4 is an aromatic ring group and the others are hydrogen atoms, and that one of R1 and R2 and one of R3 and R4 are combined to form an aromatic ring structure and the others are hydrogen atoms. The latter is more preferable.

[0082] Furthermore, examples of aromatic rings in the aromatic ring structure formed by the combination of R1 to R4 include, for example, aromatic rings such as benzene rings and naphthalene rings. The aromatic ring structure may contain only one aromatic ring or multiple aromatic rings. Furthermore, in the case of an aromatic ring structure having multiple aromatic rings, these multiple aromatic rings may be of the same type or different types. Moreover, the aromatic ring structure formed by the combination of R1 to R4 is not particularly limited, but it is preferable that the total number of carbon atoms is 7 or more and 60 or less. Furthermore, it is preferable that the aromatic ring structure is composed of only carbon atoms.

[0083] Furthermore, in the structural unit (Ib), m is an integer greater than or equal to 0 and less than or equal to 4, preferably 0, 1 or 2, with 0 or 1 being more preferred.

[0084] The content of structural unit (Ia) in the polymer is preferably 1 mol% or more, preferably 5 mol% or more, more preferably 10 mol% or more, more preferably 15 mol% or more, and preferably 60 mol% or less, more preferably 50 mol% or less, more preferably 40 mol% or less, and more preferably 30 mol% or less. If the content of structural unit (Ia) in the polymer is at or above the above lower limit, the patterning characteristics of the resin film formed from the resin composition containing the polymer can be improved when using cycloketone as a developer. On the other hand, if the proportion of structural unit (Ia) in the polymer is below the above-mentioned upper limit, the dielectric loss tangent of the resin film formed by the resin composition containing the polymer can be reduced, while the strength (tensile strength) of the resin film can be improved.

[0085] When the content of structural unit (Ib) in the polymer is set to 100 mol%, it is preferably 40 mol% or more, more preferably 50 mol% or more, more preferably 60 mol% or more, more preferably 70 mol% or more, and preferably 99 mol% or less, more preferably 95 mol% or less, more preferably 90 mol% or less, and more preferably 85 mol% or less. If the content of structural unit (Ib) in the polymer is at or above the above lower limit, the dielectric loss tangent of the resin film formed from the resin composition containing the polymer can be reduced, and the strength (tensile strength) of the resin film can be improved. On the other hand, if the proportion of structural unit (Ib) in the polymer is below the above-mentioned upper limit, the patterning characteristics of the resin film formed from the resin composition containing the polymer can be improved when using cyclic ketone as the developer.

[0086] [Proportion of structural unit (I)]

[0087] The content ratio of structural unit (I) in the polymer (i.e., the total content ratio of structural unit (Ia) and structural unit (Ib)) is preferably 20% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, and more preferably 60% by mass or less, when the total mass of the polymer is set to 100% by mass. If the content ratio of structural unit (I) in the polymer is within the range specified above, the coefficient of linear expansion of the resin film formed from the resin composition containing the polymer can be further reduced, while the heat resistance and strength (tensile strength) of the resin film can be further improved.

[0088] Furthermore, in this specification, the "content ratio" of each structural unit contained in the polymer can be measured using nuclear magnetic resonance (NMR) methods such as 1H-NMR or 13C-NMR.

[0089] 〈Structural Unit (II)〉

[0090] In the structural unit (II) shown by the above formula (II), X is a divalent organic group, Y is a tetravalent organic group, Z is a divalent organic group, and n is an integer greater than or equal to 0.

[0091] By including the structural unit (II) shown in the above formula (II) in the polymer of the present invention, the heat resistance and strength of the resin film formed by the resin composition containing the polymer can be improved while the coefficient of linear expansion is reduced.

[0092] Furthermore, the polymer of the present invention may contain only one structural unit (II) or may contain multiple units.

[0093] Furthermore, in the above formula (II), the n+1 Ys can be all the same or different, and the n+1 Zs can be all the same or different.

[0094] The Structure of X

[0095] In formula (II), X is a divalent organic group. Here, the divalent organic group constituting X is a group represented by, for example, any of the following formulas (Xa) to (Xc).

[0096] 『Chemical 12』

[0097] In the above formulas (Xa) to (Xc), R5 is an alkyl group, R6 is an alkyl group or an aromatic ring group, and p is an integer of 0 or more and 10 or less. The structure of the divalent organogroup constituting Z will be described later.

[0098] Furthermore, the alkyl groups that can form R5 and R6 are not particularly limited, but examples of alkyl groups having 1 or more carbon atoms and 10 or less can be given, with alkyl groups having 1 or more carbon atoms and 5 or less being preferred, and methyl and ethyl being more preferred.

[0099] Furthermore, examples of aromatic ring groups that constitute R6 include: phenyl, naphthyl, fumoniyl, anthracene, triphenyl, biphenyl, etc., which have 4 or more carbon atoms and 30 or fewer.

[0100] Furthermore, p can be any integer between 0 and 10, but it is better to be an integer between 0 and 5, even better to be an integer between 0 and 2, and even better to be 0 or 1.

[0101] The Structure of Y

[0102] In formula (II), Y is a tetravalent organic group. Here, the tetravalent organic group constituting Y is a group represented by any of the following formulas (Ya) to (Yf).

[0103] 『Transformation 13』

[0104] In the above formulas (Ya) to (Yf), R7, R8, R15 and R16 are independently hydrogen atoms, halogen atoms, alkyl or aromatic ring groups, respectively. R9 and R10 can also form a ring structure together. R9 and R10 that do not form a ring structure are independently hydrogen atoms, halogen atoms, alkyl or aromatic ring groups, respectively. R11 and R14 are independently oxygen atoms (-O-), sulfur atoms (-S-) or carbonyl groups (-C(=O)-), respectively. R12 and R13 can also form a ring structure together. R12 and R13 that do not form a ring structure are independently hydrogen atoms, halogen atoms, alkyl or aromatic ring groups, respectively. Alkyl and aromatic ring groups can also have halogen atoms as substituents. q and r are independently integers of 0 or more and 3 or less. s and t are independently integers of 0 or more and 4 or less.

[0105] Furthermore, the ring structure formed by the association of R9 and R10, and the ring structure formed by the association of R12 and R13, are not particularly limited, but for example, aromatic ring structures containing aromatic rings such as benzene rings, naphthalene rings, and genus rings are preferred, and aromatic ring structures containing genus rings are even more preferred. Moreover, the total number of carbon atoms in the aromatic ring structure or other ring structures is preferably 7 or more and 60 or less. In addition, the aromatic ring structure or other ring structures are preferably composed of only carbon atoms.

[0106] Furthermore, the (unsubstituted) alkyl groups that constitute the uncyclic structure of R9 and R10 and R12 and R13 are not particularly limited, but examples of alkyl groups having 1 or more carbon atoms and 10 or less can be given, with alkyl groups having 1 or more carbon atoms and 5 or less being preferred, and methyl and ethyl being more preferred.

[0107] Furthermore, there are no particular limitations on the (unsubstituted) aromatic ring groups that constitute the unringed R9, R10, R12, and R13. Examples include: phenyl, naphthyl, geniyl, anthracene, triphenyl, biphenyl, etc., which have 4 or more carbon atoms and less than 30 carbon atoms, with geniyl being preferred.

[0108] Furthermore, examples of halogen atoms that constitute R7 to R10, R12 to R13 and R15 to R16, as well as alkyl and aromatic ring groups that are substituents, include fluorine atoms, chlorine atoms, bromine atoms, etc.

[0109] As a specific example of a base represented by equation (Ya), a base represented by equation (Ya-1) can be given. Furthermore, as a specific example of a base represented by equation (Yb), a base represented by any one of equations (Yb-1) to (Yb-2) can be listed. Furthermore, as a specific example of a base represented by equation (Yc), a base represented by any one of equations (Yc-1) to (Yc-2) can be listed. Furthermore, as a specific example of a base represented by equation (Yd), a base represented by any one of equations (Yd-1) to (Yd-3) can be listed. Furthermore, as a specific example of a base represented by equation (Ye), a base represented by any one of equations (Ye-1) to (Ye-2) can be listed. Furthermore, as a specific example of a base represented by equation (Yf), a base represented by any one of equations (Yf-1) to (Yf-2) can be listed.

[0110] 『Chemistry 14』

[0111] Moreover, from the viewpoint of reducing the dielectric loss tangent of the resin film formed from the resin composition containing the polymer, the tetravalent organic group constituting Y is preferably a group represented by formula (Ye) or (Yf), preferably a group represented by formula (Ye-2), (Yf-1) or (Yf-2), and even more preferably a group represented by formula (Ye-2).

[0112] The Structure of Z

[0113] In formula (II), Z is a divalent organic group. Here, the divalent organic group constituting Z is, for example, a group represented by any of the following formulas (Za) to (Zf).

[0114] 『Transformation 15』

[0115] In the above formulas (Za) to (Zf), R17, R18, R24 and R25 are independently hydrogen atoms, halogen atoms, alkyl or aromatic ring groups, respectively; R19 and R26 are independently oxygen atoms (-O-), sulfur atoms (-S-) or carbonyl groups (-C(=O)-), respectively; R20 and R21 can also form a ring structure together; R20 and R21 that do not form a ring structure are independently hydrogen atoms, halogen atoms, alkyl or aromatic ring groups, respectively; R22 and R23 can also form a ring structure together; R22 and R23 that do not form a ring structure are independently hydrogen atoms, halogen atoms, alkyl or aromatic ring groups, respectively; alkyl and aromatic ring groups can also have halogen atoms as substituents; u, v, w and x are independently integers of 0 or more and 4 or less.

[0116] Furthermore, the ring structure formed by the association of R20 and R21, and the ring structure formed by the association of R22 and R23, are not particularly limited, but for example, aromatic ring structures containing aromatic rings such as benzene rings, naphthalene rings, and genus rings are preferred, and aromatic ring structures containing genus rings are even more preferred. Moreover, the total number of carbon atoms in the aromatic ring structure or other ring structures is preferably 7 or more and 60 or less. In addition, the aromatic ring structure or other ring structures are preferably composed of only carbon atoms.

[0117] Furthermore, the (unsubstituted) alkyl group that constitutes R17 and R18, R24 and R25 and R20 to R23 without forming a ring structure is not particularly limited, but examples of alkyl groups having 1 or more carbon atoms and 10 or less can be given, with alkyl groups having 1 or more carbon atoms and 5 or less being preferred, and methyl and ethyl being more preferred.

[0118] Furthermore, there are no particular limitations on the (unsubstituted) aromatic ring groups that constitute R17 and R18, R24 and R25 and R20 to R23 that do not form a ring structure. Examples include: phenyl, naphthyl, geniyl, anthraceneyl, triphenyl, biphenyl, etc., which have 4 or more carbon atoms and less than 30 carbon atoms, with geniyl being preferred.

[0119] Furthermore, examples of halogen atoms that constitute R17 to R18 and R20 to R25, as well as alkyl and aromatic ring groups that are substituents, include fluorine atoms, chlorine atoms, bromine atoms, etc.

[0120] As a specific example of a base represented by equation (Za), a base represented by equation (Za-1) can be given. Furthermore, as a specific example of a base represented by equation (Zb), a base represented by equation (Zb-1) can be given. Moreover, as a specific example of a base represented by equation (Zc), a base represented by any one of equations (Zc-1) to (Zc-6) can be listed. Furthermore, as a specific example of a base represented by equation (Zd), a base represented by equation (Zd-1) can be given. Furthermore, as a specific example of a base represented by equation (Ze), a base represented by equation (Ze-1) can be given. Furthermore, as a specific example of a base represented by equation (Zf), a base represented by any one of equations (Zf-1) to (Zf-3) can be listed.

[0121] 『Transformation 16』

[0122] Moreover, from the viewpoint of further improving the strength (tensile strength) of the resin film formed from the resin composition containing the polymer, the divalent organic group constituting Z is preferably a group represented by formula (Zc) or (Zf), preferably a group represented by formula (Zc-3), (Zc-4), (Zc-5), (Zc-6), (Zf-1), (Zf-2) or (Zf-3), and even more preferably a group represented by formula (Zc-3), (Zc-4), (Zc-5), (Zc-6), (Zf-2) or (Zf-3).

[0123] 《n》

[0124] Furthermore, in formula (II), n can be any integer greater than or equal to 0, but is generally greater than or equal to 1, preferably greater than or equal to 3, more preferably greater than or equal to 5, and even more preferably greater than or equal to 8. It is generally less than or equal to 100, preferably less than or equal to 80, more preferably less than or equal to 50, and even more preferably less than or equal to 30. If n in formula (II) is greater than or equal to the lower limit mentioned above, the coefficient of linear expansion of the resin film formed from the resin composition containing the polymer can be further reduced, while the heat resistance and strength (tensile strength) of the resin film can be further improved. On the other hand, if n in formula (II) is less than or equal to the upper limit mentioned above, the dielectric loss tangent of the resin film formed from the resin composition containing the polymer can be reduced.

[0125] [Containment ratio of structural unit (II)]

[0126] The content of structural unit (II) in the polymer is preferably 20% by mass or more, more preferably 30% by mass or more, more preferably 40% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, and more preferably 60% by mass or less, when the total mass of the polymer is set to 100% by mass. If the content of structural unit (II) in the polymer is within the range specified above, the coefficient of linear expansion of the resin film formed from the resin composition containing the polymer can be further reduced, and the heat resistance and strength (tensile strength) of the resin film can be further improved.

[0127] [Mass ratio of structural unit (I) to structural unit (II)]

[0128] The mass ratio of structural unit (I) to structural unit (II) in the polymer (structural unit (I) / structural unit (II)) is preferably 1 / 4 or more, more preferably 3 / 7 or more, more preferably 2 / 3 or more, and preferably 4 / 1 or less, more preferably 7 / 3 or less, and more preferably 3 / 2 or less. If the mass ratio of structural unit (I) to structural unit (II) in the polymer is within the range specified above, the dielectric loss tangent of the resin film formed from the resin composition containing the polymer can be reduced, while the heat resistance and strength (tensile strength) of the resin film can be improved.

[0129] [Concentration of amide groups in structural unit (II)]

[0130] The concentration of amide groups in structural unit (II) is preferably 13% by mass or more, more preferably 14% by mass or more, more preferably 15% by mass or more, and preferably 20% by mass or less, more preferably 19% by mass or less, and more preferably 18% by mass or less. If the concentration of amide groups in structural unit (II) is at or above the lower limit mentioned above, the strength of the resin film formed from the resin composition containing the polymer can be further improved. On the other hand, if the concentration of amide groups in structural unit (II) is at or below the upper limit mentioned above, the dielectric loss tangent of the resin film formed from the resin composition containing the polymer can be reduced.

[0131] 〈Properties of Polymers〉

[0132] Weight Average Molecular Weight

[0133] The weight-average molecular weight (Mw) of the polymer is preferably 3,000 or more, more preferably 5,000 or more, more preferably 10,000 or more, further preferably 15,000 or more, especially preferably 18,000 or more, and preferably 500,000 or less, more preferably 300,000 or less, even more preferably 100,000 or less, further preferably 60,000 or less, and especially preferably 40,000 or less. If the weight-average molecular weight of the polymer is above or below the aforementioned lower limit, the strength (tensile strength) of the resin film formed from the resin composition can be further improved. On the other hand, if the weight-average molecular weight of the polymer is below or below the aforementioned upper limit, the solubility of the resin film formed from the resin composition for the cyclic ketone used as a developer can be improved. Therefore, the patterning characteristics of the resin film can be improved when using the cyclic ketone as a developer.

[0134] Molecular Weight Distribution

[0135] The molecular weight distribution (Mw / Mn) of the polymer is preferably below 4.0, and even more preferably below 3.0. If the molecular weight distribution of the polymer is below 4.0, the patterning properties can be improved.

[0136] Furthermore, in this specification, the term "molecular weight distribution (Mw / Mn)" refers to the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn). Moreover, the weight average molecular weight and number average molecular weight of the polymer can be determined in polystyrene equivalent form by gel permeation chromatography (GPC).

[0137] (Method for manufacturing polymers)

[0138] The method for manufacturing the polymer of the present invention is characterized by comprising a step of performing a ring-opening polymerization reaction of a norethene monomer (I′) represented by the following formula (I′) and a polyimide compound (II′) represented by the following formula (II′) (hereinafter referred to as the "ring-opening polymerization step").

[0139] 『Chemical 17』・・・(I′) In formula (I′), two of R1 to R4 can also form a ring structure together. R1 to R4 that do not form a ring structure are independently hydrogen atoms, alkyl groups or aromatic ring groups. Alkyl groups and aromatic ring groups can also have hydroxyl groups as substituents. m is an integer of 0 or more and 4 or less.

[0140] 『Chemistry 18』・・・(II′) In formula (II′), X is a divalent organic group, Y is a tetravalent organic group, Z is a divalent organic group, and n is an integer greater than or equal to 0.

[0141] Furthermore, according to the polymer manufacturing method of the present invention, the polymer of the present invention described above can be manufactured efficiently. That is, according to the polymer manufacturing method of the present invention, a polymer capable of preparing a resin composition can be manufactured efficiently, wherein the resin composition forms a resin film with excellent heat resistance and strength and a low coefficient of linear expansion.

[0142] Furthermore, the method for manufacturing the polymer of the present invention generally includes a step of obtaining a ring-opening polymer hydride by hydrogenating the ring-opening polymer obtained in the above-described ring-opening polymerization step (hydrogenation step). Preferably, the method for manufacturing the polymer of the present invention further includes a step of introducing a free radical crosslinking group into the ring-opening polymer hydride obtained in the above-described hydrogenation step (hereinafter referred to as the "modification step"). Moreover, the method for manufacturing the polymer of the present invention may also optionally further include a step of synthesizing the above-described polyimide compound (II′) before the above-described ring-opening polymerization step (polyimide compound synthesis step).

[0143] The following details each process.

[0144] 〈Ring-opening polymerization process〉

[0145] In the ring-opening polymerization step, a ring-opening polymerization reaction is carried out between the norethene monomer (I′) shown in formula (I′) and the polyimide compound (II′) shown in formula (II′) to obtain a ring-opening polymer. Alternatively, monomers other than the norethene monomer (I′) and the polyimide compound (II′) may be added as needed to carry out the ring-opening polymerization reaction.

[0146] 《Norhexene Monomers (I′)》

[0147] The norethene monomer (I′) shown in the above formula (I′) is a monomer that forms the structural unit (I) described in the "Polymers" section above. Therefore, the structure of R1 to R4 and the preferred range of m in the above formula (I′) can be defined as the same as the structure of R1 to R4 and the preferred range of m in the structural unit (I) described in the same section above. However, in the norethene monomer (I′), R1 to R4 in the above formula (I′) are all defined as non-radical crosslinking groups.

[0148] For example, in manufacturing a polymer that includes both structural unit (Ia) and structural unit (Ib) as described in the same item above as structural unit (I), as a norethene monomer (I′), a monomer that forms structural unit (Ia) (hereinafter referred to as "norethene monomer (Ia′)") and a monomer that forms structural unit (Ib) (hereinafter referred to as "norethene monomer (Ib′)") can be used.

[0149] [Norepinene monomers (Ia′)]

[0150] Herein, examples of norethene monomers (Ia′) include: 2-norethene-5-methanol, 2-methyl-2-hydroxymethylbicyclo[2.2.1]hept-5-ene, 2,3-dihydroxymethylbicyclo[2.2.1]hept-5-ene, 3-hydroxytricyclo[5.2.1.0 2,6]deca-4,8-diene, 3-hydroxymethyltricyclo[5.2.1.0 2,6]deca-4,8-diene, 4-hydroxytetracyclo[6.2.1.1 3,6.0 2,7]dodecyl-9-ene, 4-hydroxymethyltetracyclo[6.2.1.1 3,6.0 2,7]dodecyl-9-ene (common name: "tetracyclododecylmethanol"), 4,5-dihydroxymethyltetracyclo[6.2.1.1 3,6.0 2,7]dodecyl-9-ene. [2,7] Dodecyl-9-ene, etc. Norbenzene monomers (Ia′) can be used alone or in combination of multiple types.

[0151] [Norepinene monomers (Ib′)]

[0152] As a norethene monomer (Ib′), examples include: tetracyclo[4.4.0.1 2,5.1 7,10]dodecyl-3-ene (common name: tetracyclododecene), 8-ethylidene tetracyclo[4.4.0.1 2,5.1 7,10]dodecyl-3-ene (common name: ethylidene tetracyclododecene), tricyclo[5.2.1.0 2,6]dec-3,8-diene (common name: bicyclopentadiene), 1,4-methylbridged-1,4,4a,9a-tetrahydrofuran (common name: methylbridged tetrahydrofuran), 5-ethylidene bicyclo[2.2.1]hept-2-ene (common name: ethylidene northoene), bicyclo[2.2.1]hept-2-ene (also known as "northoene"), 5-ethylbicyclo[2.2.1]hept-2-ene, 5-butylbicyclo[2.2.1]hept-2-ene, 5-methylenebicyclo[2.2.1]hept-2-ene, 5-vinylbicyclo[2.2.1]hept-2-ene, tetracyclo[10.2.1.0 2,11.0 4,9]pentadecano-4,6,8,13-tetraene, 9-methyltetracyclo[6.2.1.1 3,6.0 [2,7]dodecyl-4-ene, 9-ethyltetracyclo[6.2.1.1 3,6.0 2,7]dodecyl-4-ene, 9-methylenetetracyclo[6.2.1.1 3,6.0 2,7]dodecyl-4-ene, 9-ethyltetracyclo[6.2.1.1 3,6.0 2,7]dodecyl-4-ene, 9-vinyltetracyclo[6.2.1.1 3,6.0 2,7]dodecyl-4-ene, 9-propenyltetracyclo[6.2.1.1 3,6.0 2,7]dodecyl-4-ene, pentacyclic[9.2.1.1 3,9.0 2,10.0 4,8]pentadecan-5,12-diene, 9-phenyltetracyclo[6.2.1.1 3,6.0 2,7]dodecyl-4-ene, tetracyclo[9.2.1.0 [2,10.0 3,8]tetradecyl-3,5,7,12-tetraene, pentacyclic [9.2.1.1 3,9.0 2,10.0 4,8]pentadecano-12-ene, 5-phenylbicyclo[2.2.1]hept-2-ene (common name: phenylnorhexene), and their derivatives. Furthermore, the term "derivative" refers to a ring structure containing substituents. Examples of substituents that may be present in the ring structure include: alkyl, alkylene, vinyl, alkoxycarbonyl, and alkylene groups. Moreover, the ring structure of a derivative may contain one or more of these substituents.

[0153] Moreover, the norethene monomers (Ib′) can be used alone or in combination.

[0154] Polyimine Compound (II′)

[0155] The polyimide compound (II′) shown in the above formula (II′) is a compound that forms the structural unit (II) described in the "Polymers" section above. Moreover, the structures of X, Y and Z in the above formula (II′) and the preferred range of n can be defined as the same as the structures of X, Y and Z and the preferred range of n in the structural unit (II) described in the same section above.

[0156] In addition, polyimide compounds (II′) can be used alone or in combination.

[0157] [Concentration of amide groups in polyamide compound (II′)]

[0158] The concentration of amide groups in the polyamide compound (II′) is preferably 13% by mass or more, more preferably 14% by mass or more, more preferably 15% by mass or more, and preferably 20% by mass or less, more preferably 19% by mass or less, and more preferably 18% by mass or less. If the concentration of amide groups in the polyamide compound (II′) is at or above the lower limit mentioned above, the strength of the resin film formed from the resin composition containing the polymer can be further improved. On the other hand, if the concentration of amide groups in the polyamide compound (II′) is at or below the upper limit mentioned above, the dielectric loss tangent of the resin film formed from the resin composition containing the polymer can be reduced.

[0159] Furthermore, as described above, the concentration of amide groups in the polyamide compound (II′) is generally set to be consistent with the concentration of amide groups in the structural unit (II) contained in the polymer manufactured using the polymer of the present invention.

[0160] Furthermore, the details of the synthesis method of polyimide compound (II′) will be described again in the section on "synthesis process of polyimide compound".

[0161] Ring-opening polymerization reaction

[0162] Ring-opening polymerization can be carried out in a reaction solvent using well-known methods.

[0163] At this time, the reaction solvent is not particularly limited, and organic solvents such as tetrahydrofuran and toluene can be used.

[0164] Furthermore, as a molecular weight adjuster, the following can also be used: ethylene; α-olefins having 3 or more carbon atoms and less than 20, such as propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; non-conjugated dienes such as 1,4-hexadiene, 1,5-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and 1,7-octadiene; etc.

[0165] Furthermore, as an open-ring polymerization catalyst, a metal catalyst containing metals such as molybdenum, tungsten, and ruthenium can be used, among which a metal catalyst containing ruthenium is preferred.

[0166] Furthermore, the ring-opening polymerization time is usually more than 1 hour and less than 10 hours, preferably more than 2 hours and less than 5 hours. Moreover, the ring-opening polymerization temperature is usually more than 20°C and less than 100°C, preferably less than 90°C.

[0167] <Hydrogenation Process>

[0168] In the hydrogenation process, a ring-opening polymer hydride is obtained by hydrogenating the ring-opening polymer obtained in the above-described ring-opening polymerization process. The ring-opening polymer hydride obtained in the hydrogenation process is a polymer containing the structural unit (I) (except that in formula (I), R1 to R4 are other than free radical crosslinking groups) and structural unit (II) as described in the item "Polymer" above.

[0169] The hydrogenation reaction can be carried out using well-known methods. Furthermore, the hydrogenation reaction time, temperature, and pressure are not particularly limited, but the hydrogenation reaction time is generally between 1 hour and 10 hours, preferably less than 5 hours. The hydrogenation reaction temperature is generally between 100°C and 200°C, preferably less than 180°C. And the hydrogenation pressure is generally between 1 MPa and 10 MPa.

[0170] 〈Modification Process〉

[0171] In the modification process, by subjecting the ring-opening polymer hydride obtained in the ring-opening polymerization and hydrogenation process to a modification reaction caused by a modifier, a polymer is obtained in which at least one of R1 to R4 in formula (I) described in the above "polymer" item is a free radical crosslinking group, and a polymer is obtained in which the structural unit (I) and structural unit (II) are included.

[0172] Modifier

[0173] The modifier used in the modification reaction can be appropriately selected based on the desired free radical crosslinking group structure of the structural unit (I) described in the "Polymer" section above. In addition, one modifier can be used alone or multiple modifiers can be used in combination.

[0174] When introducing a free radical crosslinking group having a styrene skeleton, as a modifier, a compound having a styrene skeleton (styrene-based modifier) ​​having a functional group (halogen group, toluenesulfonyl group, methanesulfonyl group, etc.) that can undergo a modification reaction with a functional group (hydroxyl group, etc.) possessed by an open-ring polymer hydride can be used. Examples of styrene-based modifiers include: 2-(fluoromethyl)styrene, 3-(fluoromethyl)styrene, 4-(fluoromethyl)styrene, 2-(chloromethyl)styrene, 3-(chloromethyl)styrene, 4-(chloromethyl)styrene, 2-(bromomethyl)styrene, 3-(bromomethyl)styrene, 4-(bromomethyl)styrene, 2-(iodomethyl)styrene, 3-(iodomethyl)styrene, 4-(iodomethyl)styrene, halogenated methylstyrene, 2-(toluenesulfonylmethyl)styrene, 3-(toluenesulfonylmethyl)styrene, 4-(toluenesulfonylmethyl)styrene, 2-(methanesulfonylmethyl)styrene, 3-(methanesulfonylmethyl)styrene, 4-(methanesulfonylmethyl)styrene, etc. These can be used alone or in combination. From the viewpoint of efficiently carrying out the modification reaction, 4-(chloromethyl)styrene and 4-(bromomethyl)styrene are preferred.

[0175] When introducing a free radical crosslinking group having an acrylate backbone, a compound having an acrylate backbone and a functional group (halogen group, carboxylic anhydride group, etc.) that can undergo a modification reaction with a functional group (hydroxyl group, etc.) possessed by an open-ring polymer hydride can be used as a modifier (acrylate-based modifier). Examples of acrylate-based modifiers include acrylamide chloride, acrylic anhydride, methacrylic anhydride, and methacrylic anhydride. One of these can be used alone or in combination. Moreover, from the viewpoint of efficiently carrying out the modification reaction, acrylamide chloride and methacrylic anhydride are preferred.

[0176] ―Procedure and conditions for the modification reaction―

[0177] The procedure and conditions of the modification reaction are not particularly limited. For example, they can be appropriately set according to the type of modifier used. In addition, the reaction solvent in the modification reaction is not particularly limited. For example, the same reaction solvent used in the ring-opening polymerization reaction can be used.

[0178] When using, for example, a styrene-based modifier as the modifier, the modification reaction can be carried out, for example, by reacting the ring-opening polymer hydride with the styrene-based modifier in a reaction solvent in the presence of a base. In this case, the base is not particularly limited and can be: hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; hydroxides of alkaline earth metals such as calcium hydroxide; alkoxides such as lithium tributoxy, sodium tributoxy, and potassium tributoxy; triethylamine; pyridine; diacryldicycloundecene; diacryldicyclononene; and tetramethylguanidine. From the viewpoint of efficiently carrying out the modification reaction, the use of alkoxides such as lithium tributoxy, sodium tributoxy, and potassium tributoxy is preferred.

[0179] When using a styrene-based modifier as the modifier, it is preferable to use a compound that can become a source of iodide ions, such as potassium iodide and tetrabutylammonium iodide, as the catalyst. By incorporating such a catalyst, the reaction in the modification process can be promoted. The incorporation ratio of the catalyst that generates iodide ions is, for example, 1.0 part by mass and 10.0 parts by mass and less per 100 parts by mass of the ring-opening polymer hydride.

[0180] When using styrene-based modifiers as modifiers, the modification reaction temperature and modification reaction time are not particularly limited, but the modification reaction temperature is usually above -10℃ and below 100℃, and the modification reaction time is usually above 1 hour and below 15 hours.

[0181] Furthermore, when using an acrylate-based modifier as the modifier, the modification reaction can be carried out by reacting the ring-opening polymer hydride with the acrylate-based modifier in a reaction solvent in the presence of a modification reaction catalyst. In this case, the modification reaction catalyst is not particularly limited, and can be, for example, triethylamine, pyridine, etc. Furthermore, when using an acrylate-based modifier as the modifier, the modification reaction temperature and modification reaction time are not particularly limited, but the modification reaction temperature is generally between -10°C and 30°C, and the modification reaction time is generally between 1 hour and 15 hours.

[0182] 〈Polyimine Compound Synthesis Process〉

[0183] The method for manufacturing the polymer of the present invention may also include a polyimide compound synthesis step for synthesizing polyimide compound (II′) before the ring-opening polymerization step described above.

[0184] The method of synthesizing polyimide compound (II′) is not particularly limited, but for example, it can be synthesized by reacting a tetracarboxylic acid dianhydride (Y′) as shown in formula (Y′), a diamine (Z′) as shown in formula (Z′), and an end sealant (X′) as shown in formula (X′).

[0185] 『Chemical 19』

[0186] In the above formula (X′), X is a divalent organic group; in the above formula (Y′), Y is a tetravalent organic group; and in the above formula (Z′), Z is a divalent organic group.

[0187] Furthermore, the structures of X, Y and Z in the above formulas (X′), (Y′) and (Z′) can be defined as being the same as the structures of X, Y and Z in the structural unit (II) described in the above "Polymer" item.

[0188] Specifically, the polyimide compound (II′) can be synthesized by the following two-stage method as shown in the formula below: after obtaining the polyamide (II′′) shown in formula (II′′) by ring-opening superaddition reaction of tetracarboxylic dianhydride (Y′), diamine (Z′) and sealant (X′) (first stage reaction), the obtained polyamide (II′′) is subjected to cyclization dehydration reaction (second stage reaction).

[0189] 『Transformation 20』

[0190] The ring-opening addition reaction can be carried out in the reaction solvent by a well-known method.

[0191] Ring-opening addition reaction, for example, can be carried out in organic solvents such as tetrahydrofuran, γ-butyrolactone, and N-methylpyrrolidone by mixing tetracarboxylic dianhydride (Y′), diamine (Z′) and sealant (X′).

[0192] The reaction time of the ring-opening superaddition reaction is not particularly limited, but is, for example, more than 2 hours and less than 48 hours. Furthermore, the reaction temperature of the ring-opening superaddition reaction is not particularly limited, but is, for example, more than 0°C and less than 70°C.

[0193] The cyclization dehydration reaction can be carried out using well-known methods. For example, the cyclization dehydration reaction can be carried out by heating polyacrylic acid to induce cyclization, or by chemical cyclization of polyacrylic acid with a cyclization dehydrating agent. However, it is preferable to carry out the cyclization dehydration reaction by chemical cyclization.

[0194] The cyclization dehydration reaction caused by chemical acetylation can be carried out by adding a cyclization dehydration agent composed of acetic anhydride and pyridine, acetic anhydride and triethylamine to polyacrylic acid in an organic solvent such as tetrahydrofuran and mixing them together.

[0195] The reaction time of the cyclization dehydration reaction caused by chemical amide imidization is not particularly limited, but is, for example, more than 2 hours and less than 48 hours. Furthermore, the reaction temperature of the cyclization dehydration reaction caused by chemical amide imidization is not particularly limited, but is, for example, more than 0°C and less than 50°C.

[0196] (Resin composition)

[0197] The resin composition of the present invention must be included in the polymer of the present invention described above, and may include at least one of the group consisting of free radical initiators, solvents and other additives.

[0198] Since the resin composition of the present invention contains the polymer of the present invention described above, it is able to form a resin film with excellent heat resistance and strength and a low coefficient of linear expansion.

[0199] <Free Radical Initiator>

[0200] When using a polymer having free radical crosslinking groups as the polymer of the present invention described above, it is preferable that the resin composition of the present invention further contains a free radical initiator. If the resin composition contains a free radical initiator in addition to the polymer having free radical crosslinking groups, it is suitable to use a photosensitive resin composition that has decreased solubility in the developer at the exposure site and leaves a negative image at the exposure site due to development, and it can especially exhibit excellent patterning properties when using cyclic ketones as the developer.

[0201] The free radical initiator is a component that generates free radicals due to exposure or heating when using resin composition to obtain resin film, causing free radical crosslinking reaction and crosslinking of polymer.

[0202] Herein, as a free radical initiator, for example, a photoradioactive free radical generator, a thermal free radical generator, etc., can be used. Furthermore, a single free radical initiator or multiple in combination can be used. Moreover, a photoradioactive free radical generator is preferred as a free radical initiator.

[0203] Photoradical Generators

[0204] As a photoradical generator, acetylsylphosphine oxide-based, oxime ester-based, or aromatic ketone-based photoradical generators can be used. One photoradical generator can be used alone or in combination. From the viewpoint of improving exposure sensitivity while simultaneously increasing the residual film yield after development, using an oxime ester-based photoradical generator is preferred.

[0205] As a phosphine oxide-based photoradical generator, for example, bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, diphenyl(2,4,6-trimethylbenzyl)phosphine oxide, 2,4,6-trimethylbenzylphenylethoxyphosphine oxide, etc. can be used.

[0206] As an oxime ester-based photoradical generator, for example: 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzyloxime) (manufactured by BASF, distributed in the form of "Irgacure (registered trademark) OXE01"); acetone-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazole-3-yl]-1-(O-acetyloxime) (manufactured by BASF, distributed in the form of "Irgacure OXE02"); and a compound manufactured by BASF and distributed in the form of "Irgacure OXE03" (chemical formula not disclosed), etc.

[0207] Furthermore, as an aromatic ketone-based photoradical generator, the following can be used: diphenyl ketone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-prop-1-one, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethyl-1-one, 2-benzyl-2-dimethylamino-1-[4-(N-α-linyl)phenyl]but-1-one, 2-hydroxy-2-methyl-1-phenylprop-1-one, 2-methyl-1-[4-methylthiophenyl]-2-(N-α-linyl)prop-1-one, methyl o-benzylbenzyl acid, 4-(4-methylphenylthio)diphenyl ketone, 1,4-dibenzylphenyl, 2-benzylnaphthalene, 4-benzylbiphenyl, 4-benzyldiphenyl ether, diphenylethylene glycol, etc.

[0208] Content of Free Radical Initiators

[0209] Furthermore, the content of the free radical initiator in the resin composition of the present invention is preferably 0.3 parts by mass or more per 100 parts by mass of polymer, more preferably 1 part by mass or more, and preferably 25 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less. If the content of the free radical initiator in the resin composition is 0.3 parts by mass or more per 100 parts by mass of polymer, the patterning characteristics of the resin film formed from the resin composition can be further improved when using cycloketone as a developer. On the other hand, if the content of the free radical initiator in the resin composition is 25 parts by mass or less per 100 parts by mass of polymer, the dielectric loss tangent of the resin film formed from the resin composition can be reduced.

[0210] 〈Solvent〉

[0211] Any solvent may be included in the resin composition of the present invention, as long as it is soluble in the polymer of the present invention described above, and there are no particular limitations. Known solvents may be used.

[0212] Moreover, from the viewpoint of improving the coatability of the resin composition and the uniformity of the formed resin film by good solubility in the polymer of the present invention described above, it is preferable to use ketone solvents such as methyl ethyl ketone, diisobutyl ketone, cyclopentanone, and cyclohexanone, or ether solvents such as dibutyl ether, diisopentanone, tetrahydrofuran, tetrahydropiperanone, methyltetrahydropiperanone, cyclopentylmethyl ether, and methoxybenzene as solvents. It is even more preferable to use cyclopentanone, cyclohexanone, tetrahydrofuran, tetrahydropiperanone, methyltetrahydropiperanone, or methoxybenzene, and even more preferable to use methoxybenzene.

[0213] These solvents can be used alone or in combination.

[0214] Moreover, the solvent content in the resin composition is preferably such that the total amount of solvents other than solvents is 10% by mass or more, 20% by mass or more, 60% by mass or less, and 50% by mass or less relative to the total mass of the resin composition.

[0215] 〈Added Ingredients〉

[0216] Furthermore, the additives that may be included in the resin composition of the present invention are not particularly limited, and examples include: crosslinking agents, surfactants, antioxidants, sensitizers, and adhesion promoters. These additives may be used individually or in combination. From the viewpoint of improving the coatability of the resin composition of the present invention and improving the uniformity of the obtained resin film thickness, it is preferable to include surfactants as additives.

[0217] There are no particular limitations on the surfactant used; well-known polysiloxane surfactants, fluorinated surfactants, etc., can be used. Moreover, the proportion of surfactant in the resin composition is preferably 0.1% by mass or less relative to the total mass of the resin composition, and more preferably 0.05% by mass or less.

[0218] <Preparation Method of Resin Composition>

[0219] The resin composition of the present invention can be prepared by mixing the polymer of the present invention described above with various arbitrary components through known methods. Here, the resin composition of the present invention, for example, can be used in the form of a resin composition obtained by dissolving each component in a solvent and filtering. When dissolving in a solvent, known mixers such as stirrers, ball mills, sand mills, bead mills, pigment dispersers, pulverizers, ultrasonic dispersers, homogenizers, planetary mixers, and film gyratory mixers (FILMIX) can be used. Furthermore, when filtering, general filtration methods using filter media such as filters can be employed.

[0220] (Electronic Components)

[0221] The electronic component of the present invention comprises a resin film formed by the resin composition of the present invention as described above. The electronic component of the present invention is high-performance because it comprises a resin film formed by the resin composition of the present invention, which has excellent heat resistance and strength and a low coefficient of linear expansion.

[0222] The electronic components of the present invention are not particularly limited. For example, they can be manufactured by forming a resin film on a substrate such as a silicon wafer on which semiconductor elements are mounted, using the resin composition of the present invention described above.

[0223] Furthermore, the formation of the resin film on the substrate can be carried out in accordance with known resin film formation methods (for example, International Publication No. 2015 / 033901).

[0224] Furthermore, when using a polymer containing free radical crosslinking groups as the resin composition of the present invention described above, there are no particular limitations on the formed resin film. An exposure process and a development process involving irradiation with any active energy line, such as exposure light with a wavelength of 200 nm or more and 500 nm or less, can be performed to form a resin film with a desired pattern (i.e., patterned). In particular, even when cyclopentanone, cyclohexanone, or other cycloketones are used as the developer in the development process, the resin film can efficiently form the desired pattern shape. In addition, a pre-baking process can be performed before the exposure process or a post-exposure baking (PEB) process can be performed at a desired time after the start of the exposure process, depending on requirements. Furthermore, a post-baking process can be performed after the development process, depending on requirements.

[0225] The present invention will be specifically described below with reference to embodiments, but the present invention is not limited to these embodiments. In addition, in the following description, unless otherwise noted, the terms "%" and "parts" indicating quantity are based on mass.

[0226] The various measurements and evaluations in the synthesis examples, examples and comparative examples were performed using the following methods.

[0227] 〈Concentration of amide groups in polyamide compounds〉

[0228] The concentration of amide groups in polyamide compounds is calculated using the following formula.

[0229] Calculation formula: Imino concentration [%] = 100 × (molar mass of imino groups [g / mol] × molar mass of imino groups in polyimide compound [mol]) / (amount of tetracarboxylic dianhydride [g] + amount of diamine [g] + amount of end sealant [g] - amount of dehydration condensation water [g])

[0230] In addition, in the above calculation formula, "nimodiamine" means a trivalent organic group as shown in the following formula (V): 『Chemical 21』・・・(V), "molar mass of nimodiamine" is calculated in the form of 70.0 [g / mol], "mass of nimodiamine in polyimide compound" means the mass of nimodiamine contained in polyimide compound obtained under the assumption that all the monomers (tetracarboxylic dianhydride, diamine and end sealant) react and dehydrate condense, and "amount of dehydration condensation water" means the amount of water generated under the assumption that all the monomers react and dehydrate condense.

[0231] 〈Weight-average molecular weight and molecular weight distribution〉

[0232] For the polyimide compound obtained in the synthesis example and the polymer obtained in the examples and 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.

[0233] Specifically, a gel permeation chromatography system (Tosoh Corporation, "HLC-8220") was used, with columns connected to Tosoh Corporation's "TSKgel G4000HXL", "TSKgel G2000HXL", and "TSKgel G1000HXL" as the column, and tetrahydrofuran as the precipitate. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymer were determined using standard polystyrene conversion values. Then, the molecular weight distribution (Mw / Mn) was calculated.

[0234] <Tensile Strength>

[0235] On a 4-inch silicon wafer with a 50 nm thick aluminum film formed using a sputtering apparatus (manufactured by SHIBAURA ELETEC CORPORATION, "i-Miller CFS-4EP-LL"), the resin composition prepared in each example and comparative example was spin-coated onto the wafer. The wafer was then pre-baked at 90°C for 2 minutes using a hot plate to form a resin film. After exposure at 1000 mJ / cm² using a photomask alignment machine, the wafer was heated at 230°C for 1 hour in nitrogen 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 to etch the aluminum, thereby peeling the resin film off the wafer. The wafer was then dried in an oven at 110°C for 1 hour.

[0236] The dried resin film was cut into strips 5 mm wide and 40 mm long to form test pieces. Tensile tests were performed on these test pieces to measure the tensile strength of the resin film. Specifically, a tensile testing machine (Shimadzu Corporation, "AGS-10kNX") was used at 23°C with a clamp spacing of 20 mm and a tensile speed of 2 mm / min. The tensile strength at the point of fracture was measured. For resin films formed using the resin compositions obtained in each embodiment and comparative example, eight test pieces were tested, and the average of the three largest points was defined as the tensile strength. A higher tensile strength indicates better strength (mechanical strength) of the resin film, making it less prone to cracking during temperature cycling tests or drop impact tests, which is desirable. A: Tensile strength 85 MPa or higher B: Tensile strength 70 MPa or higher but less than 85 MPa C: Tensile strength less than 70 MPa

[0237] 〈Dielectric Loss Tangent〉

[0238] On a 4-inch silicon wafer with a 50 nm thick aluminum film formed using a sputtering apparatus (manufactured by SHIBAURA ELETEC CORPORATION, "i-Miller CFS-4EP-LL"), the resin composition prepared in each example and comparative example was spin-coated onto the wafer. The wafer was then pre-baked at 90°C for 2 minutes using a hot plate to form a resin film composed of the resin composition. Subsequently, the wafer was exposed using a photomask alignment machine (manufactured by Canon, "PLA501F") with a g-h-i mixed line at an irradiation dose of 1000 mJ / cm², and then heated at 180°C in nitrogen for 1 hour to cure the resin film, thereby 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 to etch aluminum, thereby peeling the resin film off the silicon wafer. After drying in an oven at 110°C for 1 hour, the sample was cut into strips 2 mm wide and 50 mm long to form test pieces. The dielectric loss tangent of these test pieces was measured at 10 GHz using the cavity resonator method. The dielectric loss tangent of the resin film was evaluated according to the following criteria: A: Dielectric loss tangent less than 0.005; B: Dielectric loss tangent greater than or equal to 0.005 but less than 0.007; C: Dielectric loss tangent greater than or equal to 0.007.

[0239] 〈Glass Transfer Temperature, Coefficient of Linear Expansion〉

[0240] On a 4-inch silicon wafer with a 50 nm thick aluminum film formed using a sputtering apparatus (manufactured by SHIBAURA ELETEC CORPORATION, "i-Miller CFS-4EP-LL"), the resin composition prepared in each embodiment and comparative example was spin-coated, and then pre-baked at 90°C for 2 minutes using a hot plate to form a film made of the resin composition. After exposure at 1000 mJ / cm² using a photomask alignment machine, the wafer was heated at 230°C for 1 hour in nitrogen to obtain a resin film, resulting in a silicon wafer with a 10 μm thick resin film. The wafer was then immersed in a 0.1 mol% hydrochloric acid aqueous solution for 12 hours to etch the aluminum, thereby peeling the resin film off the wafer, and then dried in an oven at 110°C for 1 hour. The sample was cut into strips 5 mm wide and 40 mm long to form test pieces. These test pieces underwent thermomechanical analysis (Mettler-Toledo, "TMA / SDTA841") to measure the glass transition temperature. Furthermore, the coefficient of linear expansion from 30°C to the glass transition point was calculated. The values ​​of the glass transition temperature and the coefficient of linear expansion were evaluated according to the following criteria. A higher glass transition temperature indicates better heat resistance of the resin film.

[0241] Glass Transfer Point: A: Above 160℃; B: Above 140℃ but below 160℃; C: Below 140℃

[0242] Coefficient of Linear Expansion: A: Less than 70 ppm / ℃; B: 70 ppm / ℃ or higher but less than 80 ppm / ℃; C: 80 ppm / ℃ or higher.

[0243] 〈Patterning Characteristics〉

[0244] After spin-coating the resin compositions prepared in each embodiment and comparative example onto a 4-inch silicon wafer, pre-baking was performed at 90°C for 2 minutes using a hot plate to form a resin film composed of the resin composition. Subsequently, using a photomask alignment machine (manufactured by Canon, "PLA501F") with a g-h-i mixing line, a photomask with a hole pattern of 50 μm diameter was exposed at an irradiation dose of 700 mJ / cm², and then immersed in cyclopentanone for 90 seconds for development. The presence or absence of openings in the hole pattern was confirmed using an optical microscope. Those with hole patterns were evaluated as having "openings".

[0245] 〈Tension Elongation〉

[0246] On a 4-inch silicon wafer with a 50 nm thick aluminum film formed using a sputtering apparatus (manufactured by SHIBAURA ELETEC CORPORATION, "i-Miller CFS-4EP-LL"), the resin composition prepared in each example and comparative example was spin-coated onto the wafer. The wafer was then pre-baked at 90°C for 2 minutes using a hot plate to form a resin film. After exposure at 1000 mJ / cm² using a photomask alignment machine, the wafer was heated at 230°C under nitrogen 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 to etch aluminum, thereby peeling the resin film off the wafer. The wafer was then dried in an oven at 110°C for 1 hour.

[0247] The dried resin film was cut into strips 5 mm wide and 40 mm long to form test pieces. Tensile tests were performed on these test pieces to measure the elongation at break. Specifically, a tensile testing machine (Shimadzu Corporation, "AGS-10kNX") was used at 23°C with a clamp spacing of 20 mm and a tensile speed of 2 mm / min. The elongation at break was measured. For resin films formed using the resin compositions obtained in each embodiment and comparative example, tests were performed on 8 test pieces, and the average of the three largest points was defined as the elongation at break. A higher elongation at break indicates better ductility of the resin film, which helps suppress crack formation during temperature cycling tests or drop impact tests, and is less prone to peeling. A: Elongation at break 20% or more B: Elongation at break 10% or more but less than 20% C: Elongation at break less than 10%

[0248] (Synthesis Example 1)

[0249] <Synthesis of polyimide compound (A-1)> (Composition: BPADA / HFBAPP / 4ASt)

[0250] Under a nitrogen stream, 400 g of dehydrated tetrahydrofuran was placed in a 1 L three-necked flask, and then 51.5 g of 4,4′-(4,4′-isopropylidenediphenoxy)diphthalic anhydride (hereinafter simply referred to as "BPADA"), which is a tetracarboxylic dianhydride, was added and dissolved. Next, 46.6 g of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (hereinafter simply referred to as "HFBAPP"), which is a diamine, and 2.4 g of 4-aminostyrene (hereinafter simply referred to as 4ASt), which is a terminal sealing agent, were added and reacted at room temperature for 12 hours. Subsequently, 31.3 g of pyridine and 47.5 g of acetic anhydride were added, and after further stirring for 12 hours, 300 g of tetrahydrofuran, which is a solvent, was added to the reaction solution and diluted. This was dropped into 8 L of methanol, and the resulting precipitate was recovered by filtration and dried under reduced pressure at 70°C for 10 hours, thereby obtaining a polyimide compound (A-1) represented by the following formula (A-1). The weight average molecular weight of the polyimide compound (A-1) was 19,800, and the molecular weight distribution was 1.4. Moreover, the calculated value of the imide group concentration in the polyimide compound (A-1) was 14.4%.

[0251] 'Chemical formula 22'... (A-1)

[0252] (Synthesis Example 2)

[0253] 〈Synthesis of polyimide compound (A-2)〉(Composition: BPADA / BAPP / 4ASt)

[0254] Except that in Synthesis Example 1, the addition amount of BPADA was changed from 51.5 g to 58.1 g, 36.6 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (hereinafter simply referred to as "BAPP") was added instead of 46.6 g of HFBAPP, the addition amount of 4ASt was changed from 2.4 g to 5.3 g, the addition amount of pyridine was changed from 31.3 g to 35.3 g, and the addition amount of acetic anhydride was changed from 47.5 g to 54.0 g, the operation was carried out in accordance with Synthesis Example 1, and a polyimide compound (A-2) represented by the following formula (A-2) was obtained. The weight average molecular weight of the polyimide compound (A-2) was 9,900, and the molecular weight distribution was 1.6. Moreover, the calculated value of the imide group concentration in the polyimide compound (A-2) was 16.0%.

[0255] 'Chemical formula 23'... (A-2)

[0256] (Synthesis Example 3) Synthesis of Polyimide Compound (A-3) (Composition: a-BPDA / HFBAPP / 4ASt)

[0258] Except in Synthesis Example 1, 37.5 g of 2,3,3′,4′-biphenyltetracarboxylic dianhydride (hereinafter abbreviated as "a-BPDA") was added instead of 51.5 g of BPADA, the addition amount of HFBAPP was changed from 46.6 g to 59.5 g, the addition amount of 4ASt was changed from 2.4 g to 3.0 g, the addition amount of pyridine was changed from 31.3 g to 34.6 g, and the addition amount of acetic anhydride was changed from 47.5 g to 53.0 g. Otherwise, the operation was carried out according to Synthesis Example 1 to obtain the polyimide compound (A-3) represented by the following formula (A-3). The weight average molecular weight of the polyimide compound (A-3) was 9900, and the molecular weight distribution was 1.8. Moreover, the calculated value of the imide group concentration in the polyimide compound (A-3) was 18.7%.

[0259] 'Chemical Formula 24'... (A-3)

[0260] In addition, Formula (A-3) is ultimately only an example of the structure of the polyimide compound (A-3) obtained through Synthesis Example 3 above. For example, the polyimide compound (A-3) may also have a structure in Formula (A-3) in which at least a part of the structure derived from a-BPDA represented by the following formula (a): 'Chemical Formula 25'... (a) is reversed left and right, that is, a structure replaced by the structure represented by the following formula (a'): 'Chemical Formula 26'... (a').

[0261] (Synthesis Example 4) Synthesis of Polyimide Compound (A-4) (Composition: BPADA / BAFL / 4ASt)

[0263] Except in Synthesis Example 1, the addition amount of BPADA was changed from 51.5 g to 60.7 g, 46.6 g of HFBAPP was changed to 36.6 g of 9,9-bis(4-aminophenyl)fluorene (hereinafter abbreviated as "BAFL"), the addition amount of 4ASt was changed from 2.4 g to 2.8 g, the addition amount of pyridine was changed from 31.3 g to 36.4 g, and the addition amount of acetic anhydride was changed from 47.5 g to 57.4 g. Otherwise, the operation was carried out according to Synthesis Example 1 to obtain the polyimide compound (A-4) represented by the following formula (A-4). The weight average molecular weight of the polyimide compound (A-4) was 16000, and the molecular weight distribution was 1.5. Moreover, the calculated value of the imide group concentration in the polyimide compound (A-4) was 17.0%.

[0264] Chemical formula 27... (A-4)

[0265] (Synthesis Example 5)

[0266] 〈Synthesis of Polyimide Compound (A-5)〉(Composition: BPAF / HFBAPP / 4ASt)

[0267] Except in Synthesis Example 1, 48.3 g of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (hereinafter abbreviated as "BPAF".) was added instead of 51.5 g of BPADA, the addition amount of HFBAPP was changed from 46.6 g to 49.2 g, the addition amount of 4ASt was changed from 2.4 g to 2.5 g, the addition amount of pyridine was changed from 31.3 g to 33.3 g, and the addition amount of acetic anhydride was changed from 47.5 g to 52.3 g. The operation was carried out in accordance with Synthesis Example 1 to obtain polyimide compound (A-5). The weight average molecular weight of polyimide compound (A-5) was 16,100, and the molecular weight distribution was 1.6. Moreover, the calculated value of the imide group concentration in polyimide compound (A-5) was 15.3%.

[0268] Chemical formula 28... (A-5)

[0269] (Synthesis Example 6)

[0270] 〈Synthesis of Polyimide Compound (A-6)〉(Composition: BPADA / BPAF / HFBAPP / 4ASt = 0.5 / 0.5 / 0.9 / 2.0 (molar ratio))

[0271] Except in Synthesis Example 1, the addition amount of BPADA was changed from 51.5 g to 26.2 g, 23.1 g of BPAF was added, the addition amount of HFBAPP was changed from 46.6 g to 48.2 g, the addition amount of 4ASt was changed from 2.4 g to 2.5 g, the addition amount of pyridine was changed from 31.3 g to 31.8 g, and the addition amount of acetic anhydride was changed from 47.5 g to 50.8 g. The operation was carried out in accordance with Synthesis Example to obtain polyimide compound (A-6) represented by the following formula (A-6). The weight average molecular weight of polyimide compound (A-6) was 17,000, and the molecular weight distribution was 1.8. Moreover, the calculated value of the imide group concentration in polyimide compound (A-6) was 14.8%.

[0272] Chemical formula 29... (A-6)

[0273] In addition, in formula (A-6), A refers to any of the following.

[0274] 『Transformation 30』

[0275] (Example 1) (Composition: MTF / NBMOH / (BPADA / HFBAPP / 4ASt), MTF / NBMOH = 70 / 30)

[0276] <Polymer Manufacturing>

[0277] Ring-opening polymerization process, hydrogenation process

[0278] 92.9 parts of polyimide compound (A-1), 100 parts of a monomer mixture consisting of 30 mol% of 2-norphene-5-methanol (hereinafter referred to as "NBMOH") as a norphene monomer (Ia) and 70 mol% of methyl-bridged tetrahydrofuran (hereinafter referred to as "MTF") as a norphene monomer (Ib), 0.4 parts of dichlorobenzyl[1,3-bis(2,4,6-trimethylyl)-2-imidazolinediyl] (tricyclohexylphosphine)ruthenium as a ring-opening polymerization catalyst, and 900 parts of tetrahydrofuran as a solvent were placed in a nitrogen-purged glass pressure reactor and reacted at 50°C for 4 hours with stirring to obtain a polymerization reaction solution.

[0279] The obtained polymerization reaction solution was placed in an autoclave and stirred for 5 hours at 130°C and 10 MPa for hydrogenation reaction. Then, 900 parts of tetrahydrofuran as a solvent were added to the reaction solution. It was then added dropwise to 8000 parts of methanol. The resulting precipitate was recovered by filtration and dried under reduced pressure at 50°C to obtain the ring-opening polymer hydride (B-1) as a polymer. The weight average molecular weight of the ring-opening polymer hydride (B-1) was 33,100, and the molecular weight distribution was 1.9.

[0280] 『Transformation 31】

[0281] <Preparation of Resin Composition>

[0282] 100 parts of the ring-opening polymer hydride (B-1) obtained as described above, and methoxybenzene (solvent), in an amount equal to 30% of the total mass of the resin composition, were mixed to dissolve the polymer. Subsequently, KP-341 (manufactured by Shin-Etsu Silicon Power Co., Ltd.) was added as a polysiloxane surfactant in an amount equal to 0.03% of the total mass of the resin composition, and the resin composition was prepared by filtering through a polytetrafluoroethylene filter with a pore size of 0.45 μm.

[0283] Then, using the obtained resin composition, various evaluations were performed as described above. The results are shown in Table 1.

[0284] (Example 2) (Composition: MTF / NBMOH / (BPADA / HFBAPP / 4ASt), MTF / NBMOH = 85 / 15)

[0285] Except that the open-ring polymer hydride (B-2) manufactured by the following operation was used instead of the open-ring polymer hydride (B-1) in the preparation of the resin composition of Example 1, the resin composition was prepared in accordance with the operation of Example 1.

[0286] Then, using the obtained resin composition, various evaluations were performed as described above. The results are shown in Table 1.

[0287] <Polymer Manufacturing>

[0288] Except that in the preparation of the polymer in Example 1, the amount of compound (A-1) added was changed to 112.2 parts, the amount of NBMOH added was changed to 15 mol%, and the amount of MTF added was changed to 85 mol%, the same procedure as in Example 1 was followed to obtain the ring-opening polymer hydride (B-2) as a polymer (refer to the formula below). The weight average molecular weight of the ring-opening polymer hydride (B-2) was 33,000, and the molecular weight distribution was 1.9.

[0289] 『Transformation 32】

[0290] (Example 3) (Composition: MTF / NBMOH-MA / (BPADA / BAPP / 4ASt), Mohrbi (MTF / NBMOH-MA) = 70 / 30)

[0291] <Polymer Manufacturing>

[0292] Ring-opening polymerization process, hydrogenation process

[0293] 103.0 parts of polyimide compound (A-2), 100 parts of a monomer mixture consisting of 30 moles of NBMOH as a norethene monomer (Ia) and 70 moles of MTF as a norethene monomer (Ib), 0.4 parts of dichlorobenzyl[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolinide] (tricyclohexylphosphine)ruthenium as a ring-opening polymerization catalyst, and 900 parts of tetrahydrofuran as a solvent were placed into a nitrogen-purged glass pressure reactor and reacted at 50°C for 4 hours with stirring to obtain a polymerization reaction solution.

[0294] The obtained polymerization reaction solution was placed in an autoclave and stirred for 5 hours at 130°C and 10 MPa for hydrogenation reaction. Then, 900 parts of tetrahydrofuran as a solvent were added to the reaction solution. It was then added dropwise to 8000 parts of methanol. The resulting precipitate was recovered by filtration and dried under reduced pressure at 50°C to obtain the ring-opening polymer hydride (B-3). The weight average molecular weight of the ring-opening polymer hydride (B-3) was 17900, and the molecular weight distribution was 1.6.

[0295] "Modification Process"

[0296] A three-necked flask equipped with a stirrer and thermometer was purged with nitrogen. 100 parts of the ring-opening polymer hydride (B-3), 89.8 parts of triethylamine as a catalyst for the modification reaction, and 500 parts of tetrahydrofuran as a solvent were added. The reaction solution was cooled to 0°C in an ice bath. The temperature of the reaction solution was maintained below 10°C, and 54.6 parts of methacrylamide chloride as a modifier were added dropwise while stirring for 2 hours. Next, the reaction solution was heated to room temperature and stirred continuously for 12 hours. Subsequently, 200 parts of tetrahydrofuran as a solvent were added to the reaction solution, which was then cooled to 0°C. Methanol, in parts by mass equal to 0.5 times that of methacrylamide chloride, was added, while the temperature of the reaction solution was maintained below 10°C. The solution was kept at 0°C for 1 hour, then heated to room temperature and stirred for another hour.

[0297] The reaction solution was added dropwise to 8000 parts of methanol, and the resulting precipitate was recovered by filtration. The precipitate was washed three times with methanol and then dried under reduced pressure at 50°C to obtain the modified ring-opening polymer hydride (hereinafter referred to as "modified ring-opening polymer hydride") (C-3) (refer to the formula below). The weight average molecular weight of the modified ring-opening polymer hydride (C-3), measured by GPC, was 14400, and the molecular weight distribution was 1.5.

[0298] 1H-NMR measurement confirmed that the methacrylyl modification rate of the ring-opening polymer hydride (B-3) was 100%. The proportion of structural units derived from methacrylyl-modified NBMOH in the modified ring-opening polymer hydride (C-3) was 30 mol% when the total content of structural units derived from MTF and structural units derived from methacrylyl-modified NBMOH (hereinafter sometimes abbreviated as "NBMOH-MA") was set at 100 mol%.

[0299] 『Transformation 33』

[0300] 〈Preparation of Resin Composition〉

[0301] 100 parts of the modified ring-opening polymer hydride (C-3) obtained as a polymer as described above, 5 parts of "Irgacure OXE01" (manufactured by BASF) as a free radical initiator, and methoxybenzene (solvent) in an amount equal to 30% of the total mass of the resin composition were mixed and dissolved. Subsequently, KP-341 (manufactured by Shin-Etsu Silicon Power Co., Ltd.) as a polysiloxane surfactant was added at a rate of 0.03% of the total mass of the resin composition, and the resin composition was prepared by filtration through a polytetrafluoroethylene filter with a pore size of 0.45 μm.

[0302] Then, using the obtained resin composition, various evaluations were performed as described above. The results are shown in Table 1.

[0303] (Example 4) (Composition: MTF / NBMOH-MA / (BPADA / HFBAPP / 4ASt), Mohrbi (MTF / NBMOH-MA) = 70 / 30)

[0304] Except that the modified ring-opening polymer hydride (C-1) prepared by the following operation was used instead of the modified ring-opening polymer hydride (C-3) in the preparation of the resin composition of Example 3, the resin composition was prepared in accordance with the operation of Example 3.

[0305] Then, using the obtained resin composition, various evaluations were performed as described above. The results are shown in Table 1.

[0306] <Polymer Manufacturing>

[0307] "Quality Modification Process"

[0308] A three-necked flask equipped with a stirrer and thermometer was purged with nitrogen. 100 parts of the ring-opening polymer hydride (B-1) obtained in Example 1 above, 95.3 parts of triethylamine as a catalyst for the modification reaction, and 500 parts of tetrahydrofuran as a solvent were added. The reaction solution was cooled to 0°C in an ice bath. The temperature of the reaction solution was maintained below 10°C, and 59.1 parts of methacrylamide chloride as a modifier were added dropwise while stirring for 2 hours. Next, the reaction solution was heated to room temperature and stirred continuously for 12 hours. Subsequently, 200 parts of tetrahydrofuran as a solvent were added to the reaction solution, which was then cooled to 0°C. Methanol, in an amount 0.5 times the mass of methacrylamide chloride, was added, and the temperature of the reaction solution was maintained below 10°C. The solution was then heated to room temperature and stirred for another hour.

[0309] The reaction solution was added dropwise to 8000 parts of methanol, and the resulting precipitate was recovered by filtration. The precipitate was washed three times with methanol and then dried under reduced pressure at 50°C to obtain the modified ring-opening polymer hydride (hereinafter referred to as "modified ring-opening polymer hydride") (C-1) (refer to the formula below). The weight average molecular weight of the modified ring-opening polymer hydride (C-1), measured by GPC, was 22600, and the molecular weight distribution was 1.5.

[0310] By 1H-NMR measurement, it was confirmed that the methacrylyl modification rate of the ring-opening polymer hydride (B-1) was 100%, and the proportion of structural units derived from methacrylyl-modified NBMOH in the modified ring-opening polymer hydride (C-1) was 30 mol when the total content of structural units derived from MTF and structural units derived from methacrylyl-modified NBMOH was set at 100 mol%.

[0311] 『Transformation 34』

[0312] (Example 5) (Composition: MTF / NBMOH-MA / (BPADA / HFBAPP / 4ASt), Mohrbi (MTF / NBMOH-MA) = 85 / 15)

[0313] Except that the modified ring-opening polymer hydride (C-2) prepared by the following operation was used instead of the modified ring-opening polymer hydride (C-3) in the preparation of the resin composition of Example 3, the resin composition was prepared in accordance with the operation of Example 3.

[0314] Then, using the obtained resin composition, various evaluations were performed as described above. The results are shown in Table 1.

[0315] <Polymer Manufacturing>

[0316] "Quality Modification Process"

[0317] A three-necked flask equipped with a stirrer and thermometer was purged with nitrogen. 100 parts of the ring-opening polymer hydride (B-2) obtained in Example 2 above, 41.6 parts of triethylamine as a catalyst for the modification reaction, and 500 parts of tetrahydrofuran as a solvent were added. The reaction solution was cooled to 0°C in an ice bath. The temperature of the reaction solution was maintained below 10°C, and 25.5 parts of methacrylic chloride as a modifier were added dropwise while stirring for 2 hours. Next, the reaction solution was heated to room temperature and stirred continuously for 12 hours. Subsequently, 200 parts of tetrahydrofuran as a solvent were added to the reaction solution, which was then cooled to 0°C. Methanol, in parts by mass equal to 0.5 times that of methacrylic chloride, was added, and the temperature of the reaction solution was maintained below 10°C. The solution was then heated to room temperature for 1 hour and stirred for another hour.

[0318] The reaction solution was added dropwise to 8000 parts of methanol, and the resulting precipitate was recovered by filtration. The precipitate was washed three times with methanol and then dried under reduced pressure at 50°C to obtain the modified ring-opening polymer hydride (hereinafter referred to as "modified ring-opening polymer hydride") (C-2) (refer to the formula below). The modified ring-opening polymer hydride (C-2) has a weight average molecular weight of 25200 and a molecular weight distribution of 1.5.

[0319] By 1H-NMR measurement, it was confirmed that the methacrylyl modification rate of the ring-opening polymer hydride (B-2) was 100%, and the proportion of structural units derived from methacrylyl-modified NBMOH in the modified ring-opening polymer hydride (C-2) was 15 mol when the total content of structural units derived from MTF and structural units derived from methacrylyl-modified NBMOH was set at 100 mol%.

[0320] 『Transformation 35】

[0321] (Example 6) (Composition: MTF / NBMOH-MA / (a-BPDA / HFBAPP / 4ASt), Mohrbi (MTF / NBMOH-MA) = 70 / 30)

[0322] Except that the modified ring-opening polymer hydride (C-4) prepared by the following operation was used instead of the modified ring-opening polymer hydride (C-3) in the preparation of the resin composition of Example 3, the resin composition was prepared in accordance with the operation of Example 3.

[0323] Then, using the obtained resin composition, various evaluations were performed as described above. The results are shown in Table 2.

[0324] <Polymer Manufacturing>

[0325] Ring-opening polymerization process, hydrogenation process

[0326] Except that 92.6 parts of polyimide compound (A-3) were added in place of 103.0 parts of polyimide compound (A-2) in the ring-opening polymerization and hydrogenation processes of the polymer manufacturing in Example 3, the ring-opening polymer hydrogenation (B-4) was obtained by following the procedure in Example 3.

[0327] "Quality Modification Process"

[0328] Except that in the modification process of manufacturing the polymer in Example 3, ring-opening polymer hydride (B-4) was added instead of ring-opening polymer hydride (B-3), the amount of triethylamine added was changed from 89.8 parts to 99.6 parts, and the amount of methacrylic acid chloride added was changed from 54.6 parts to 58.8 parts, the modified ring-opening polymer hydride (C-4) as a polymer was obtained by following the same procedure as in Example 3 (refer to the formula below). The weight average molecular weight of the modified ring-opening polymer hydride (C-4) measured by GPC was 14,100, and the molecular weight distribution was 1.6.

[0329] By 1H-NMR measurement, it was confirmed that the methacrylyl modification rate of the ring-opening polymer hydride (B-4) was 100%, and the proportion of structural units derived from methacrylyl-modified NBMOH in the modified ring-opening polymer hydride (C-4) was 30 mol when the total content of structural units derived from MTF and structural units derived from methacrylyl-modified NBMOH was set at 100 mol%.

[0330] 『Transformation 36』

[0331] (Example 7) (Composition: MTF / NBMOH-MA / (BPADA / BAFL / 4ASt), Mohrbi (MTF / NBMOH-MA) = 70 / 30)

[0332] Except that the modified ring-opening polymer hydride (C-5) prepared by the following operation was used instead of the modified ring-opening polymer hydride (C-3) in the preparation of the resin composition of Example 3, the resin composition was prepared in accordance with the operation of Example 3.

[0333] Then, using the obtained resin composition, various evaluations were performed as described above. The results are shown in Table 2.

[0334] <Polymer Manufacturing>

[0335] Ring-opening polymerization process, hydrogenation process

[0336] Except that 100.7 parts of polyimide compound (A-4) were added in place of 103.0 parts of polyimide compound (A-2) in the ring-opening polymerization and hydrogenation processes of the polymer manufacturing in Example 3, the ring-opening polymer hydrogenation (B-5) was obtained by following the procedure in Example 3.

[0337] "Quality Modification Process"

[0338] Except that in the modification process of manufacturing the polymer in Example 3, ring-opening polymer hydride (B-5) was added instead of ring-opening polymer hydride (B-3), the amount of triethylamine added was changed from 89.8 parts to 96.0 parts, and the amount of methacrylic acid chloride added was changed from 54.6 parts to 56.2 parts, the modified ring-opening polymer hydride (C-5) as a polymer was obtained by following Example 3 (refer to the formula below). The modified ring-opening polymer hydride (C-5) has a weight average molecular weight of 19,600 and a molecular weight distribution of 1.6.

[0339] By 1H-NMR measurement, it was confirmed that the methacrylyl modification rate of the ring-opening polymer hydride (B-5) was 100%, and the proportion of structural units derived from methacrylyl-modified NBMOH in the modified ring-opening polymer hydride (C-5) was 30 mol when the total content of structural units derived from MTF and structural units derived from methacrylyl-modified NBMOH was set at 100 mol%.

[0340] 『Transformation 37】

[0341] (Example 8) (Composition: MTF / NBMOH-MA / (BPAF / HFBAPP / 4ASt), Mohrbi (MTF / NBMOH-MA) = 70 / 30)

[0342] Except that the modified ring-opening polymer hydride (C-6) prepared by the following operation was used instead of the modified ring-opening polymer hydride (C-3) in the preparation of the resin composition of Example 3, the resin composition was prepared in accordance with the operation of Example 3.

[0343] Then, using the obtained resin composition, various evaluations were performed as described above. The results are shown in Table 2.

[0344] <Polymer Manufacturing>

[0345] Ring-opening polymerization process, hydrogenation process

[0346] Except that 106.6 parts of polyimide compound (A-5) were added instead of 103.0 parts of polyimide compound (A-2) in the ring-opening polymerization and hydrogenation processes of the polymer manufacturing in Example 3, the ring-opening polymer hydrogenation (B-6) was obtained by following the procedure in Example 3.

[0347] "Quality Modification Process"

[0348] Except that in the modification process of manufacturing the polymer in Example 3, ring-opening polymer hydride (B-6) was added instead of ring-opening polymer hydride (B-3), the amount of triethylamine added was changed from 89.8 parts to 91.9 parts, and the amount of methacrylic acid chloride added was changed from 54.6 parts to 53.3 parts, the modified ring-opening polymer hydride (C-6) as a polymer was obtained by following Example 3 (refer to the formula below). The modified ring-opening polymer hydride (C-6) has a weight average molecular weight of 38,300 and a molecular weight distribution of 2.4.

[0349] By 1H-NMR measurement, it was confirmed that the methacrylyl modification rate of the ring-opening polymer hydride (B-6) was 100%, and the proportion of structural units derived from methacrylyl-modified NBMOH in the modified ring-opening polymer hydride (C-6) was 30 mol when the total content of structural units derived from MTF and structural units derived from methacrylyl-modified NBMOH was set at 100 mol%.

[0350] 『Transformation 38】

[0351] (Comparative Example 1) (Composition: MTF / NBMOH-MA = 70 / 30)

[0352] Except that the open-ring polymer hydride (B-7) manufactured by the following operation was used instead of the open-ring polymer hydride (B-1) in the preparation of the resin composition of Example 1, the resin composition was prepared in accordance with the operation of Example 1.

[0353] Then, using the obtained resin composition, various evaluations were performed as described above. The results are shown in Table 2.

[0354] <Polymer Manufacturing>

[0355] Ring-opening polymerization process, hydrogenation process

[0356] 100 parts of a monomer mixture consisting of 30 moles of NBMOH and 70 moles of MTF, 1.0 part of 1,5-hexadiene as a molecular weight adjuster, 0.2 parts of dichlorobenzyl[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolinediyl](tricyclohexylphosphine)ruthenium as a ring-opening polymerization catalyst, and 300 parts of tetrahydrofuran as a reaction solvent were placed in a nitrogen-purged glass pressure reactor and reacted at 80°C for 4 hours with stirring to obtain a polymerization reaction solution.

[0357] The obtained polymerization reaction solution was placed in an autoclave and stirred for 5 hours at 130°C and 10 MPa for hydrogenation. Then, 300 parts of tetrahydrofuran were added to the reaction solution as a solvent. This was then added dropwise to 8000 parts of methanol. The resulting precipitate was recovered by filtration and dried under reduced pressure at 50°C to obtain the ring-opening polymer hydride (B-7) (refer to the formula below). The weight average molecular weight of the ring-opening polymer hydride (B-7) was 38,000, and the molecular weight distribution was 2.6.

[0358] 『Transformation 39】

[0359] (Comparative Example 2) (Composition: NB / NBMOH-MA = 85 / 15)

[0360] Except that the modified addition polymer (C-8) prepared by the following operation was used instead of the modified ring-opening polymer hydride (C-3) in the preparation of the resin composition in Example 3, the resin composition was prepared in accordance with the operation in Example 3.

[0361] Then, using the obtained resin composition, various evaluations were performed as described above. The results are shown in Table 2.

[0362] <Polymer Manufacturing>

[0363] Addition Polymerization Process

[0364] Excluding the point of scaling up by 20 times, the addition polymer (B-8) of norethene and NBMOH was obtained by following the method described in Macromolecules 29, 2761 (1996).

[0365] "Quality Modification Process"

[0366] Except that in the modification step of manufacturing the polymer of Example 3, addition polymer (B-8) was added instead of ring-opening polymer hydride (B-3), the amount of triethylamine added was changed from 89.8 parts to 170.4 parts, the amount of methacrylic acid chloride added was changed from 54.6 parts to 95.3 parts, and the solvent was changed from tetrahydrofuran to toluene, the modified addition polymer (C-8) was obtained by following the procedure of Example 3 (refer to the formula below). The modified addition polymer (C-8) had a weight average molecular weight of 28,100 and a molecular weight distribution of 1.84.

[0367] By 1H-NMR measurement, it was confirmed that the methacrylyl modification rate of the addition polymer (B-8) was 100%, and the proportion of structural units derived from methacrylyl-modified NBMOH in the modified addition polymer (C-8) was 15 mol when the total content of structural units derived from norethene and structural units derived from methacrylyl-modified NBMOH was set at 100 mol%.

[0368] 『Transformation 40】

[0369] (Example 9) (Composition: MTF / NBMOH-MA / (BPADA / BPAF / HFBAPP / 4ASt), MOT (MTF / NBMOH-MA) = 70 / 30)

[0370] Except that the modified ring-opening polymer hydride (C-9) prepared by the following operation was used instead of the modified ring-opening polymer hydride (C-3) in the preparation of the resin composition of Example 3, the resin composition was prepared in accordance with the operation of Example 3.

[0371] Then, using the obtained resin composition, various evaluations were performed as described above. The results are shown in Table 3.

[0372] <Polymer Manufacturing>

[0373] Ring-opening polymerization process, hydrogenation process

[0374] Except that 117.6 parts of polyimide compound (A-6) were added in place of 103.0 parts of polyimide compound (A-2) in the ring-opening polymerization and hydrogenation processes of the polymer manufacturing in Example 3, the ring-opening polymer hydrogenation (B-9) was obtained by following the procedure in Example 3.

[0375] "Quality Modification Process"

[0376] Except that in the modification process of manufacturing the polymer in Example 3, ring-opening polymer hydride (B-9) was added instead of ring-opening polymer hydride (B-3), the amount of triethylamine added was changed from 89.8 parts to 94.5 parts, and the amount of methacrylic acid chloride added was changed from 54.6 parts to 52.4 parts, the modified ring-opening polymer hydride (C-9) as a polymer was obtained by following Example 3 (refer to the formula below). The modified ring-opening polymer hydride (C-9) had a weight average molecular weight of 34,500 and a molecular weight distribution of 2.0.

[0377] By 1H-NMR measurement, it was confirmed that the methacrylyl modification rate of the ring-opening polymer hydride (B-9) was 100%, and the proportion of structural units derived from methacrylyl-modified NBMOH in the modified ring-opening polymer hydride (C-9) was 30 mol when the total content of structural units derived from MTF and structural units derived from methacrylyl-modified NBMOH was set at 100 mol%.

[0378] 『Chemistry 41】

[0379] In addition, in the above formula, A refers to any of the following.

[0380] 『Transformation 42』

[0381] 『Table 1』 Example 1 Example 2 Example 3 Example 4 Example 5 resin composition polymer type B-1 B-2 C-3 C-1 C-2 Structural Unit (I) Composition (Mollbi) MTF / NBMOH =70 / 30 MTF / NBMOH =85 / 15 MTF / NBMOH-MA =70 / 30 MTF / NBMOH-MA =70 / 30 MTF / NBMOH-MA =85 / 15 Structural Unit (II) Composition BPADA / HFBAPP / 4ASt BPADA / HFBAPP / 4ASt BPADA / BAPP / 4ASt BPADA / HFBAPP / 4ASt BPADA / HFBAPP / 4ASt mass ratio (Structural Unit (I)) / Structural Unit (II)) 1.00 / 0.93 1.00 / 1.12 1.00 / 0.84 1.00 / 0.72 1.00 / 0.84 The presence or absence of free radical crosslinking groups in structural unit (I) none none have have have Structural Unit (II) Imino group Concentration [mass %] 14.4 14.4 16.0 14.4 14.4 Weight-average molecular weight (Mw) 33,100 33,000 14,400 22,600 25,200 Molecular weight distribution (Mw / Mn) 1.9 1.9 1.5 1.5 1.5 free radical polymerization initiators Irgacure OXE01 [Parts by weight / 100 parts by weight of polymer] — — 5 5 5 evaluate Heat resistance (Glass transfer temperature) A A A A A strength B B B B B coefficient of linear expansion A A A A A Dielectric loss tangent C B A A A Patterning characteristics — — Opening Opening Opening

[0382] 『Table 2』 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 resin Composition polymer type C-4 C-5 C-6 B-7 C-8 Structural Unit (I) Composition (Mollbi) MTF / NBMOH-MA =70 / 30 MTF / NBMOH-MA =70 / 30 MTF / NBMOH-MA =70 / 30 MTF / NBMOH =70 / 30 Additive polymerization Structural Unit (II) Composition a-BPDA / HFBAPP / 4ASt BPADA / BAFL / 4ASt BPAF / HFBAPP / 4ASt — — mass ratio (Structural Unit (I)) / Structural Unit (II)) 1.00 / 0.71 1.00 / 0.78 1.00 / 0.86 — — The presence or absence of free radical crosslinking groups in structural unit (I) have have have none have Structural Unit (II) Imino group Concentration [mass %] 18.7 17.0 15.3 — — Weight-average molecular weight (Mw) 14,100 19,600 38,300 38,000 28,100 Molecular weight distribution (Mw / Mn) 1.6 1.6 2.4 2.6 1.8 free radical polymerization initiators Irgacure OXE01 [Parts by weight / 100 parts by weight of polymer] 5 5 5 5 5 evaluate Heat resistance (Glass transfer temperature) A A A C B strength A A A C C coefficient of linear expansion A A A C C Dielectric loss tangent B A A C B Patterning characteristics Opening Opening Opening — Opening

[0383] 『Table 3』 Example 9 resin Composition polymer type C-4 Structural Unit (I) Composition (Mollbi) MTF / NBMOH-MA =70 / 30 Structural Unit (II) Composition BPADA / BPAF / HFBAPP / 4ASt mass ratio (Structural Unit (I)) / Structural Unit (II)) 1.00 / 0.91 The presence or absence of free radical crosslinking groups in structural unit (I) have Structural Unit (II) Imino group Concentration [mass %] 14.8 Weight-average molecular weight (Mw) 36,000 Molecular weight distribution (Mw / Mn) 2.0 free radical polymerization initiators Irgacure OXE01 [Parts by weight / 100 parts by weight of polymer] 5 evaluate Heat resistance (Glass transfer temperature) A strength A coefficient of linear expansion A Dielectric loss tangent A Patterning characteristics A elongation A

[0384] As can be seen from Tables 1 to 3, if a resin composition containing "polymers of Examples 1 to 9 containing specified structural units (I) and structural units (II)" is used, a resin film with excellent heat resistance and strength and a low coefficient of linear expansion can be formed.

[0385] On the other hand, it is known that when a resin composition is used that "contains polymers of Comparative Examples 1 to 2 that do not contain at least the specified structural unit (II)," the heat resistance and strength of the resin film formed are poor, and the coefficient of linear expansion is also high.

[0386] According to the present invention, a polymer capable of preparing a resin composition can be provided, the resin composition being able to form a resin film with excellent heat resistance and strength and a low coefficient of linear expansion.

[0387] Furthermore, according to the present invention, a resin composition capable of forming a resin film with excellent heat resistance and strength and a low coefficient of linear expansion can be provided.

[0388] Furthermore, according to the present invention, electronic components having the resin film can be provided. [Simplified Explanation of the Diagram]

[0039] None.

Claims

1. A polymer comprising a structural unit (I) represented by formula (I) below and a structural unit (II) represented by formula (II) below; 『Chemical 1』・・・(I) In formula (I), R1 to R4 may also form a ring structure together, and R1 to R4 that do not form a ring structure are independently hydrogen atoms, alkyl groups, aromatic ring groups or free radical crosslinking groups, and alkyl and aromatic ring groups may also have hydroxyl groups as substituents, and m is an integer of 0 or more and 4 or less; 『Chemical 2』・・・(II) In formula (II), X is a divalent organic group, Y is a tetravalent organic group, Z is a divalent organic group, and n is an integer of 0 or more.

2. The polymer as claimed in claim 1, wherein at least one of the aforementioned R1 to R4 is a free radical crosslinking group.

3. The polymer as claimed in claim 1, wherein the aforementioned X is a divalent organic group represented by any of the following formulas (Xa) to (Xc); in formulas (Xa) to (Xc), R5 is an alkyl group, R6 is an alkyl group or an aromatic group, and p is an integer of 0 or more and 10 or less.

4. The polymer as claimed in claim 1, wherein the aforementioned Y is a tetravalent organic group represented by any one of the following formulas (Ya) to (Yf); in formulas (Ya) to (Yf), R7, R8, R15 and R16 are each independently a hydrogen atom, a halogen atom, an alkyl group or an aromatic ring group, R9 and R10 may also form a ring structure together, R9 and R10 without forming a ring structure are each independently a hydrogen atom, a halogen atom, an alkyl group or an aromatic ring group, R11 and R14 are each independently an oxygen atom, a sulfur atom or a carbonyl group, R12 and R13 may also form a ring structure together, R12 and R13 without forming a ring structure are each independently a hydrogen atom, a halogen atom, an alkyl group or an aromatic ring group, the alkyl and aromatic ring groups may also have a halogen atom as a substituent, q and r are each independently an integer of 0 or more and 3 or less, and s and t are each independently an integer of 0 or more and 4 or less.

5. The polymer as claimed in claim 1, wherein the aforementioned Z is a divalent organic group represented by any of the following formulas (Za) to (Zf); in formulas (Za) to (Zf), R17, R18, R24 and R25 are each independently a hydrogen atom, a halogen atom, an alkyl group or an aromatic ring group, R19 and R26 are each independently an oxygen atom, a sulfur atom or a carbonyl group, R20 and R21 may also form a ring structure together, R20 and R21 without forming a ring structure are each independently a hydrogen atom, a halogen atom, an alkyl group or an aromatic ring group, R22 and R23 may also form a ring structure together, R22 and R23 without forming a ring structure are each independently a hydrogen atom, a halogen atom, an alkyl group or an aromatic ring group, the alkyl and aromatic ring groups may also have a halogen atom as a substituent, and u, v, w and x are each independently an integer greater than 0 and less than 4.

6. The polymer as claimed in claim 1, wherein the concentration of amide groups in the aforementioned structural unit (II) is 13% by mass or more and 20% by mass or less.

7. A resin composition comprising the polymer as described in any one of claims 1 to 6.

8. The resin composition as described in claim 7, further comprising a free radical initiator.

9. The resin composition as described in claim 7, further comprising at least one of a ketone solvent and an ether solvent.

10. The resin composition as claimed in claim 9, wherein the aforementioned ketone solvent contains at least one of cyclopentanone and cyclohexanone, and the aforementioned ether solvent contains at least one selected from the group consisting of tetrahydrofuran, tetrahydropiperanone, methyltetrahydropiperanone and methoxybenzene.

11. A method for manufacturing a polymer, comprising a step of performing a ring-opening polymerization reaction of a norethene monomer (I′) as shown in formula (I′) and a polyimide compound (II′) as shown in formula (II′); 『Chemical 6』・・・(I′) In formula (I′), R1 to R4 may also form a ring structure together, and R1 to R4 that do not form a ring structure are independently hydrogen atoms, alkyl groups or aromatic ring groups, and the alkyl and aromatic ring groups may also have hydroxyl groups as substituents, and m is an integer of 0 or more and 4 or less; 『Chemical 7』・・・(II′) In formula (II′), X is a divalent organic group, Y is a tetravalent organic group, Z is a divalent organic group, and n is an integer of 0 or more.

12. A method for manufacturing the polymer as claimed in claim 11, wherein the concentration of amide groups in the aforementioned polyamide compound (II′) is 13% by mass or more and 20% by mass or less.

13. An electronic component comprising a resin film formed from a resin composition as described in claim 6.

14. The electronic component as claimed in claim 13, wherein the aforementioned resin film is patterned.