WO2023053976A1

WO2023053976A1 - Resin composition

Info

Publication number: WO2023053976A1
Application number: PCT/JP2022/034479
Authority: WO
Inventors: 隆志堤; 耕平蒲田
Original assignee: 日本ゼオン株式会社
Priority date: 2021-09-29
Filing date: 2022-09-14
Publication date: 2023-04-06
Also published as: CN117836339A; TW202330660A; KR20240067232A; JPWO2023053976A1

Abstract

The purpose of the present invention is to provide a resin composition containing a cyclic olefin polymer, said resin composition being capable of forming a resin film that shows excellent patterning properties when a cyclic ketone is used as a developer. The resin composition of the present invention contains a cyclic olefin polymer and a radical initiator. The cyclic olefin polymer contains specific structural units (I) and (II). In the cyclic olefin polymer, the ratio of the sum of the contents of the structural units (I) and (II) in the cyclic olefin polymer is 80 mol% or more, when the amount of all structural units contained in the cyclic olefin polymer is regarded as 100 mol%.

Description

resin composition

The present invention relates to resin compositions.

Conventionally, electronic parts such as integrated circuit elements and organic EL elements have a protective film to prevent deterioration and damage to the parts themselves, a planarizing film to flatten the element surface and wiring, and a film to maintain electrical insulation. Various resin films are provided as an electrical insulation film, a pixel separation film for separating light emitting portions, an optical film for condensing and diffusing light, and the like.

In recent years, cyclic olefin polymers, which are excellent in various performances, have attracted attention as resin materials that constitute such resin films. For example, Patent Document 1 discloses a cyclic olefin polymer having a plurality of crosslinkable double bonds in the side chain portion, a predetermined polyphenylene ether, triallyl isocyanurate and/or triallyl cyanurate, and an organic peroxide. A resin composition is disclosed comprising: According to Patent Document 1, a resin film having a low dielectric loss tangent can be formed by using the resin composition described above.

JP 2018-39950 A

Here, generally, the resin film is provided with a desired pattern shape according to its use. Cyclic ketones such as cyclopentanone are widely used as developing solutions for patterning. However, even if the resin film formed using the above-mentioned conventional resin composition is exposed and the resin film after exposure is developed with a cyclic ketone, the cyclic olefin polymer is difficult to dissolve in the cyclic ketone. However, it was difficult to impart a desired pattern shape to the resin film.
That is, the conventional resin composition containing a cyclic olefin polymer has room for further improvement in terms of enhancing the patterning properties of a resin film formed from the resin composition when a cyclic ketone is used as a developer. was there.

Therefore, an object of the present invention is to provide a resin composition containing a cyclic olefin polymer, which is capable of forming a resin film having excellent patterning properties when a cyclic ketone is used as a developer.

The inventor of the present invention has diligently studied in order to achieve the above purpose. Then, the present inventor provides a resin composition comprising a cyclic olefin polymer containing two types of predetermined structural units and having a total content ratio of the two types of structural units equal to or greater than a predetermined value, and a radical initiator. The present inventors have newly found that a resin film having excellent patterning properties can be formed when a cyclic ketone is used as a developer, and have completed the present invention.

That is, an object of the present invention is to advantageously solve the above problems, and the present invention provides the following resin compositions [1] to [5].
[1] A resin composition containing a cyclic olefin polymer and a radical initiator, wherein the cyclic olefin polymer comprises a structural unit (I) represented by the following formula (I) and a structural unit (I) represented by the following formula (II): and the structural unit (II) shown, and the content ratio of the structural unit (I) in the cyclic olefin polymer when the amount of all structural units contained in the cyclic olefin polymer is 100 mol% The resin composition, wherein the total content of the structural units (II) is 80 mol% or more.

In formula (I), at least one of R ¹ to R ⁴ is a radical crosslinkable group, and each of R ¹ to R ⁴ not corresponding to a radical crosslinkable group is independently a hydrogen atom, an alkyl group, or an aromatic ring group. and two of R ¹ to R ⁴ that do not correspond to radical crosslinkable groups may combine to form a ring, and m is an integer of 0 or more and 4 or less.

In formula (II), at least one of R ⁵ to R ⁸ is an aromatic ring group, or two of R ⁵ to R ⁸ together form an aromatic ring-containing structure, and the aromatic ring group R ⁵ to R ⁸ which do not correspond and do not form an aromatic ring-containing structure are each independently a hydrogen atom or an alkyl group, and n is an integer of 0 or more and 4 or less.
According to such a resin composition, it is possible to form a resin film having excellent patterning properties when a cyclic ketone is used as a developer.
In this specification, the “content ratio” of each structural unit contained in the polymer can be measured using a nuclear magnetic resonance (NMR) method such as ¹ H-NMR and ¹³ C-NMR.

[2] The content of the structural unit (II) in the cyclic olefin polymer is 70 mol% or more when the amount of all structural units contained in the cyclic olefin polymer is 100 mol%. The resin composition according to [1].
If the content ratio of the structural unit (II) in the cyclic olefin polymer is 70 mol% or more, the dielectric loss tangent of the resin film formed from the resin composition can be lowered and the mechanical strength can be improved.

[3] The resin composition according to [1] or [2] above, wherein the radical crosslinkable group has at least one of a styryl skeleton and an acrylate skeleton.
If the structural unit (I) contains a radically crosslinkable group having a styryl skeleton, the dielectric loss tangent of the resin film formed from the resin composition is reduced, and the resin film is patterned when a cyclic ketone is used as a developer. Properties can be further enhanced. Then, if the structural unit (I) contains a radical crosslinkable group having an acrylate skeleton, the dielectric loss tangent of the resin film formed from the resin composition is reduced while the extensibility is improved, and the resin film can be used as a developer. Patterning properties can be further enhanced when cyclic ketones are used.
In this specification, the radical cross-linkable group “having a styryl skeleton” means that the radical cross-linkable group is “CH ₂ ═CH—Ph— (Ph is a phenylene group and one of the hydrogen atoms in the formula part or all of which may be substituted with any substituent)”. In this specification, the group "having a styryl skeleton" does not correspond to "aromatic ring group" but to "radical crosslinkable group".
Further, in this specification, the radical cross-linkable group “having an acrylate skeleton” means that the radical cross-linkable group is “CH ₂ ═CH—C(═O)—O— (part of the hydrogen atoms in the formula or All of which may be substituted with any substituents.)”.

[4] The resin composition according to any one of [1] to [3] above, further comprising a cross-linking agent having at least two polymerizable unsaturated bonds.
In addition to the cyclic olefin polymer and the radical initiator described above, if a resin composition containing a cross-linking agent having at least two polymerizable unsaturated bonds (hereinafter sometimes abbreviated as "cross-linking agent") is used, the resin It is possible to improve extensibility while reducing the dielectric loss tangent of the resin film formed from the composition.
In the present specification, a polymer containing a structural unit derived from a cyclic olefin, even if it has at least two polymerizable unsaturated bonds, does not correspond to a "crosslinking agent" and is referred to as a "cyclic olefin polymer. ” shall be applicable.

[5] The resin according to [4] above, wherein the cross-linking agent contains at least one of a cross-linking agent (III) represented by the following formula (III) and a cross-linking agent (IV) represented by the following formula (IV) Composition.

In formula (IV), A is a divalent organic group, and a and b are integers of 0 or more and 300 or less. Note that a and b may be the same or different, except when only one of a and b is 0.
If a resin composition containing the cross-linking agent (III) and/or the cross-linking agent (IV) is used as the cross-linking agent, the dielectric loss tangent of the resin film formed from the resin composition can be further reduced while the stretchability can be further improved. can be done.

According to the resin composition containing the cyclic olefin polymer of the present invention, it is possible to form a resin film with excellent patterning properties when a cyclic ketone is used as a developer.

Here, the resin composition of the present invention is not particularly limited, and can be used when forming resin films that can be provided in electronic components such as integrated circuit elements, organic EL elements, and semiconductor packages. In particular, the resin composition of the present invention can be suitably used when manufacturing insulating organic films such as organic EL, semiconductor packages, printed wiring boards, and solder resists. Furthermore, the resin composition of the present invention can be suitably used as a negative-type photosensitive resin composition in which the solubility of the exposed portion in the developing solution is reduced and the exposed portion remains after development. In addition, the active energy ray used when exposing the resin film formed using the resin composition of the present invention is not particularly limited, and is a single-wavelength ray such as ultraviolet rays, g-line, h-line, i-line, or the like. Light rays, light rays such as KrF excimer laser light and ArF excimer laser light, and particle beams such as electron beams can be mentioned.

(resin composition)
The resin composition of the present invention is required to contain a cyclic olefin polymer and a radical initiator, and may optionally contain at least one selected from the group consisting of a cross-linking agent, a solvent, and other additive components.

<Cyclic olefin polymer>
The cyclic olefin polymer contained in the resin composition of the present invention is a polymer capable of undergoing a cross-linking reaction by radicals generated by irradiation with active energy rays in the presence of a radical initiator.
Here, the cyclic olefin polymer includes a structural unit (I) represented by the following formula (I) and a structural unit (II) represented by the following formula (II), and all structures contained in the cyclic olefin polymer When the amount of the units is 100 mol%, the total content of the structural unit (I) and the structural unit (II) in the cyclic olefin polymer must be 80 mol% or more.

In formula (II), at least one of R ⁵ to R ⁸ is an aromatic ring group, or two of R ⁵ to R ⁸ together form an aromatic ring-containing structure, and the aromatic ring group R ⁵ to R ⁸ which do not correspond and do not form an aromatic ring-containing structure are each independently a hydrogen atom or an alkyl group, and n is an integer of 0 or more and 4 or less.

By using the resin composition of the present invention containing the cyclic olefin polymer having the composition described above, it is possible to form a resin film having excellent patterning properties when a cyclic ketone is used as the developer.
The reason why the resin film formed from the resin composition of the present invention is excellent in patterning properties when a cyclic ketone is used as a developer is not clear, but is presumed as follows.
First, the resin film obtained using the resin composition containing the cyclic olefin polymer having the composition described above is less likely to be turbid due to phase separation, and can suppress the scattering of active energy rays during exposure. . In addition, the cyclic olefin polymer having the composition described above contained in the unexposed portion of the resin film is highly soluble in the cyclic ketone used as the developer. Due to the contribution of the cyclic olefin polymer having such properties, it is believed that the use of the resin composition of the present invention enables formation of a resin film having excellent patterning properties when a cyclic ketone is used as a developer.

<<Structural unit (I)>>
In structural unit (I) represented by formula (I), at least one of R ¹ to R ⁴ is a radical crosslinkable group. R ¹ to R ⁴ which do not correspond to radical crosslinkable groups are each independently a hydrogen atom, an alkyl group or an aromatic ring group, and two of R ¹ to R ⁴ which do not correspond to radical crosslinkable groups are may form a ring. Moreover, m is an integer of 0 or more and 4 or less.
The cyclic olefin polymer may contain only one type of structural unit (I), or may contain a plurality of types.

[Radical crosslinkable group]
Here, the radical crosslinkable group that can constitute R ¹ to R ⁴ has a carbon-carbon unsaturated bond (especially an ethylenically unsaturated bond) and is caused by a radical generated by a radical initiator. There is no particular limitation as long as it is a group having a molecular skeleton capable of undergoing a radical reaction. The radical crosslinkable group preferably includes a radical crosslinkable group having a styryl skeleton and a radical crosslinkable group having an acrylate skeleton.

-Radical crosslinkable group having a styryl skeleton-
It is presumed that if the structural unit (I) of the cyclic olefin polymer has a radical crosslinkable group having a styryl skeleton, the ratio of polar atoms in the structural unit (I) is reduced. Dielectric loss tangent can be lowered. Moreover, for the resin film, patterning characteristics can be further enhanced when a cyclic ketone is used as the developer.
Here, examples of radical crosslinkable groups having a styryl skeleton include groups represented by the following formula (V).

In formula (V), X and Z are each independently a single bond or an alkylene group having 1 to 10 carbon atoms, Y is an oxygen atom or a sulfur atom, and R ⁹ is a hydrogen atom or a substituent and p is an integer of 0 or more and 4 or less.

The alkylene group having 1 to 10 carbon atoms that can be X and Z in the formula (V) is not particularly limited, but a methylene group, an ethylene group, a propylene group, an n-butylene group, an isobutylene group, or the like having 1 or more carbon atoms. A chain alkylene group of 6 or less is preferable, and a linear alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group, a propylene group, and an n-butylene group is more preferable, and a methylene group, an ethylene group, a propylene group, etc. is more preferably a linear alkylene group having 1 or more and 3 or less carbon atoms, and a methylene group is particularly preferable.

Substituents that can be R ⁹ in formula (V) include, but are not particularly limited to, alkyl groups such as methyl and ethyl groups, and halogeno groups such as fluoro and chloro groups.

In formula (V), p is preferably 0, that is, the phenylene group (--C ₆ H ₄ --) constituting the styryl skeleton preferably has no substituent.

-Radical Crosslinkable Group Having an Acrylate Skeleton-
If the structural unit (I) of the cyclic olefin polymer has a radical crosslinkable group having an acrylate skeleton, the dielectric loss tangent of the resin film formed from the resin composition can be reduced while the extensibility can be improved. Moreover, for the resin film, patterning characteristics can be further enhanced when a cyclic ketone is used as the developer.
Here, examples of radical crosslinkable groups having an acrylate skeleton include groups represented by the following formula (VI).

In formula (VI), G is an alkylene group having 1 to 10 carbon atoms, and R ¹⁰ is a hydrogen atom or an alkyl group.

In the radical crosslinkable group represented by formula (VI), the substituted or unsubstituted acryloyl group is bonded to the cyclic olefin structure via the alkylene group represented by G, so that the mobility of the acryloyl group is enhanced. there is Due to this improvement in mobility, the cross-linking reactivity of the acryloyl group is improved. Presumably for this reason, if a cyclic olefin polymer having a radically crosslinkable group represented by formula (VI) is used, the dielectric loss tangent of the resin film formed from the resin composition is reduced while the extensibility is improved. Moreover, the patterning characteristics of the resin film can be further enhanced when a cyclic ketone is used as the developer.

The alkylene group having 1 to 10 carbon atoms that can be G in the formula (VI) is not particularly limited, but is a group having 1 to 6 carbon atoms such as a methylene group, ethylene group, propylene group, n-butylene group and isobutylene group. A chain alkylene group of is preferable, a methylene group, an ethylene group, a propylene group, a linear alkylene group having 1 to 6 carbon atoms such as an n-butylene group is more preferable, a methylene group, an ethylene group, a carbon such as a propylene group A linear alkylene group having a number of 1 or more and 3 or less is more preferable, and a methylene group is particularly preferable.

The alkyl group that can be R ¹⁰ in formula (VI) is not particularly limited, and examples thereof include alkyl groups having 1 to 5 carbon atoms. Among them, the alkyl group that can constitute R ¹⁰ is preferably a methyl group or an ethyl group.

[Structure other than radical crosslinkable group]
In formula (I), the alkyl group that can constitute R ¹ to R ⁴ other than the radical crosslinkable group is not particularly limited, and examples thereof include alkyl groups having 1 to 5 carbon atoms.
In formula (I), the aromatic ring group other than the radical crosslinkable group, which may constitute R ¹ to R ⁴ , is not particularly limited as long as it does not correspond to a radical crosslinkable group, and examples thereof include a phenyl group and a naphthyl group. , fluorenyl group, anthracenyl group, triphenylenyl group, pyrenyl group, and other aromatic ring groups having 4 to 30 carbon atoms.
Also, the structure in which two of R ¹ to R ⁴ other than the radical crosslinkable group form a ring together is not particularly limited, and examples thereof include a carbocyclic ring having a monocyclic structure or a polycyclic structure.

Furthermore, in formula (I), m is an integer of 0 to 4, preferably 0, 1 or 2, more preferably 0 or 1, as described above.

[Preferred Structure of Structural Unit (I)]
In structural unit (I), one of R ¹ to R ⁴ in formula (I) is preferably a radical crosslinkable group and the others are preferably hydrogen atoms. This is because if the structural unit (I) has such a structure, the synthesis is relatively easy and the production efficiency of the resin composition is increased.

[Content ratio of structural unit (I)]
Here, the content of the structural unit (I) in the cyclic olefin polymer is preferably 1 mol% or more when the amount of all structural units contained in the cyclic olefin polymer is 100 mol%. It is more preferably 5 mol% or more, still more preferably 10 mol% or more, particularly preferably 15 mol% or more, preferably 60 mol% or less, and 50 mol% or less. is more preferably 40 mol % or less, still more preferably 30 mol % or less, and particularly preferably 20 mol % or less. If the content of the structural unit (I) in the cyclic olefin polymer is 1 mol % or more, the patterning properties of the resin film formed from the resin composition can be further enhanced when the cyclic ketone is used as the developer. can be done. On the other hand, if the content of the structural unit (I) in the cyclic olefin polymer is 60 mol % or less, the dielectric loss tangent of the resin film formed from the resin composition can be lowered while the extensibility can be improved.

<<Structural unit (II)>>
In the structural unit (II) represented by the above formula (II), at least one of R ⁵ to R ⁸ is an aromatic ring group, or two of R ⁵ to R ⁸ together form an aromatic ring-containing structure. R ⁵ to R ⁸ which do not correspond to an aromatic ring group and do not form an aromatic ring-containing structure are each independently a hydrogen atom or an alkyl group, and n is an integer of 0 or more and 4 or less. be.
The cyclic olefin polymer may contain only one type of structural unit (II), or may contain a plurality of types.

Here, the aromatic ring group that can constitute R ⁵ to R ⁸ of formula (II) is not particularly limited, but includes an aromatic ring group having 4 or more and 30 or less carbon atoms. Examples of the aromatic ring group having 4 to 30 carbon atoms include phenyl group, naphthyl group, fluorenyl group, anthracenyl group, triphenylenyl group and pyrenyl group.
Further, examples of the aromatic ring in the aromatic ring-containing structure formed by combining two of R ⁵ to R ⁸ of formula (II) include aromatic hydrocarbon rings such as benzene ring and naphthalene ring. be done. The aromatic ring-containing structure may contain only one aromatic ring, or may contain a plurality of aromatic rings. Moreover, when the aromatic ring-containing structure has a plurality of aromatic rings, the plurality of aromatic rings may be the same type of aromatic rings or different types of aromatic rings. The aromatic ring-containing structure formed by combining two of R ⁵ to R ⁸ is not particularly limited, but the total number of carbon atoms is preferably 7 or more and 60 or less. Also, the aromatic ring-containing structure is preferably composed only of carbon atoms.

In formula (II), ^the alkyl group that can constitute R ⁵ to R ⁸ which is not an aromatic ring group and does not form an aromatic ring-containing structure is not particularly limited ^. The same alkyl groups that can be composed are included.

Furthermore, in formula (II), n is an integer of 0 to 4, preferably 0, 1 or 2, more preferably 0 or 1, as described above.

[Suitable Structure of Structural Unit (II)]
Structural unit (II) reduces the dielectric loss tangent of the resin film formed from the resin composition while improving the extensibility, and further improves the patterning properties of the resin film when a cyclic ketone is used as a developer. From the point of view, one of R ⁵ to R ⁸ is an aromatic ring group and the others are hydrogen atoms, and one of R ⁵ and R ⁶ and one of R ⁷ and R ⁸ together An embodiment in which an aromatic ring-containing structure (for example, a structure containing a benzene ring) is formed and the others are hydrogen atoms is preferred, and the latter embodiment is more preferred.

[Content ratio of structural unit (II)]
Here, the content ratio of the structural unit (II) in the cyclic olefin polymer is 10 mol% or more when the amount of all structural units contained in the cyclic olefin polymer is 100 mol%. % or more, more preferably 50 mol% or more, still more preferably 70 mol% or more, particularly preferably 80 mol% or more, and 99 mol% or less. It is preferably 95 mol % or less, more preferably 90 mol % or less. If the content ratio of the structural unit (II) in the cyclic olefin polymer is 10 mol% or more, the dielectric loss tangent of the resin film formed from the resin composition is reduced and the mechanical strength (tensile strength) is improved. can be done. On the other hand, if the content of the structural unit (II) in the cyclic olefin polymer is 99 mol% or less, the resin film formed from the resin composition can further improve the patterning properties when the cyclic ketone is used as the developer. can be enhanced.

<<Total Content Ratio of Structural Unit (I) and Structural Unit (II)>>
Then, in the cyclic olefin polymer, when the sum of the content ratio of the structural unit (I) and the content ratio of the structural unit (II) is 100 mol% of the total structural units contained in the cyclic olefin polymer In addition, as described above, it is necessary to be 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, further preferably 97 mol% or more, and 99 It is more preferably mol % or more, and particularly preferably 100 mol %. When the total content of the structural unit (I) and the structural unit (II) is 80 mol% or more, the patterning properties of the resin film formed from the resin composition are ensured when a cyclic ketone is used as a developer. can do. Further, when the total content of the structural unit (I) and the structural unit (II) is 80 mol% or more, the mechanical strength (tensile strength) of the resin film formed from the resin composition can be improved.

<<Other structural units>>
The cyclic olefin polymer can optionally contain structural units (other structural units) other than the structural units (I) and (II) described above. Other structural units include, for example, structural units derived from known monomers copolymerizable with monomers capable of forming structural unit (I) and monomers capable of forming structural unit (II). can be used.
Here, the content of other structural units in the cyclic olefin polymer must be 20 mol% or less when the amount of all structural units contained in the cyclic olefin polymer is 100 mol%. . For the resin film formed from the resin composition, the content of other structural units in the cyclic olefin polymer is 10 mol% or less from the viewpoint of further improving the patterning properties when a cyclic ketone is used as a developer. is preferably 5 mol% or less, more preferably 3 mol% or less, even more preferably 1 mol% or less, and 0 mol% (i.e., cyclic olefin weight It is particularly preferred that the coalescence does not contain other structural units).

<<Properties of Cyclic Olefin Polymer>>
―Weight average molecular weight―
The weight average molecular weight (Mw) of the cyclic olefin polymer is preferably 3,000 or more, more preferably 5,000 or more, still more preferably 10,000 or more, and 500,000 or less. preferably 300,000 or less, and even more preferably 100,000 or less. If the weight average molecular weight of the cyclic olefin polymer is 3,000 or more, the mechanical strength (tensile strength) of the resin film formed from the resin composition can be increased. Moreover, when the weight average molecular weight of the cyclic olefin polymer is 500,000 or less, the solubility of the resin film formed from the resin composition in the cyclic ketone as a developer can be enhanced. As a result, the patterning characteristics of the resin film can be further improved when the cyclic ketone is used as the developer.

―Molecular weight distribution―
The molecular weight distribution (Mw/Mn) of the cyclic olefin polymer is preferably 4.0 or less, more preferably 3.0 or less. When the molecular weight distribution of the cyclic olefin polymer is 4.0 or less, it is possible to improve the resolution when the resulting resin film is patterned.
In this specification, "molecular weight distribution (Mw/Mn)" refers to the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn). The weight-average molecular weight and number-average molecular weight of the cyclic olefin polymer are obtained as polystyrene equivalent values by gel permeation chromatography (GPC).

<<Method for Synthesizing Cyclic Olefin Polymer>>
The method for synthesizing the cyclic olefin polymer described above is not particularly limited. For example, a ring-opening polymer is synthesized by a ring-opening polymerization reaction of a norbornene-based monomer, and the resulting ring-opening polymer is subjected to a hydrogenation reaction. (hereinafter referred to as “ring-opening polymerization and hydrogenation step”) and performing a modification reaction on the resulting hydrogenated ring-opening polymer, Efficient synthesis can be achieved by a method including a step of introducing a radical crosslinkable group into the hydrogenated ring polymer (hereinafter referred to as a “modification step”). Each step will be described in detail below.

[Ring-opening polymerization and hydrogenation step]
In the ring-opening polymerization and hydrogenation step, first, a norbornene-based monomer (I) capable of forming the structural unit (I) described above and a norbornene-based monomer (II) capable of forming the structural unit (II) described above ) to synthesize a ring-opening polymer by a ring-opening polymerization reaction. If necessary, a ring-opening polymerization reaction may be performed by adding a monomer other than the norbornene-based monomer (I) and the norbornene-based monomer (II).

-Norbornene monomer (I)-
Here, the norbornene monomer (I) includes, for example, 2-norbornene-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 ]dodeca-9-ene, 4-hydroxymethyltetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-9-ene (common name: “tetracyclododecenemethanol”), 4,5-dihydroxymethyltetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-9-ene and the like. Norbornene-based monomers (I) can be used singly or in combination of multiple types.

-Norbornene monomer (II)-
Examples of the norbornene monomer (II) include tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene (common name: tetracyclododecene), 8-ethylidene-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene (common name: ethylidenetetracyclododecene), tricyclo[5.2.1.0 ^2,6 ]deca-3,8-diene (common name: dicyclopentadiene), 1,4-methano-1,4,4a-9a-tetrahydrofluorene (common name: methanotetrahydrofluorene), 5-ethylidenebicyclo[2.2.1]hept-2-ene (common name: ethylidenenobornene), bicyclo[2.2.1]hept-2-ene (also referred to as "norbornene"), 5-ethyl-bicyclo[2.2.1]hept-2-ene, 5-butyl-bicyclo[2.2. 1]hept-2-ene, 5-methylidene-bicyclo[2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-2-ene, tetracyclo[10.2. 1.0 ^{2, 11} . 0 ^4,9 ]pentadeca-4,6,8,13-tetraene, 9-methyl-tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-ethyl-tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-methylidene-tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-ethylidene-tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-vinyl-tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-propenyl-tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, pentacyclo[9.2.1.1 ^3,9 . 0 ^{2, 10} . 0 ^4,8 ]pentadeca-5,12-diene, 9-phenyl-tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, tetracyclo[9.2.1.0 ^2,10 . 0 ^3,8 ]tetradeca-3,5,7,12-tetraene, pentacyclo[9.2.1.1 ^3,9 . 0 ^{2, 10} . 0 ^4,8 ]pentadeca-12-ene, 5-phenylbicyclo[2.2.1]hept-2-ene (common name: phenylnorbornene) and derivatives thereof. In addition, a derivative refers to what has a substituent in a ring structure. Substituents that may be present in the ring structure include, for example, alkyl groups, alkylene groups, vinyl groups, alkoxycarbonyl groups, and alkylidene groups. The ring structure of the derivative may have one or more of these substituents.
Norbornene-based monomers (II) can be used singly or in combination of multiple types.

The ring-opening polymerization reaction can be carried out in a reaction solvent according to a known method.
At that time, the reaction solvent is not particularly limited, and organic solvents such as tetrahydrofuran and toluene can be used, for example.
Further, as a molecular weight modifier, ethylene; 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, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1 - α-olefins having 3 to 20 carbon atoms such as octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; 1,4-hexadiene, 1,5-hexadiene , 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, and derivatives thereof;
As the ring-opening polymerization catalyst, a metal catalyst containing metals such as molybdenum, tungsten, and ruthenium can be used. Among them, it is preferable to use a metal catalyst containing ruthenium.
Furthermore, the ring-opening polymerization time is usually 1 hour or more and 10 hours or less, preferably 2 hours or more and 5 hours or less. The ring-opening polymerization temperature is usually 20° C. or higher and 100° C. or lower, preferably 90° C. or lower.

Next, the resulting ring-opening polymer is subjected to a hydrogenation reaction to synthesize a hydrogenated ring-opening polymer.
At that time, the hydrogenation reaction can be carried out according to a known method. The hydrogenation reaction time, hydrogenation reaction temperature and hydrogenation pressure in the hydrogenation reaction are not particularly limited, but the hydrogenation reaction time is usually 1 hour or more and 10 hours, preferably 5 hours or less. . Moreover, the hydrogenation reaction temperature is usually 100° C. or higher and 200° C. or lower, preferably 180° C. or lower. The hydrogenation pressure is generally 1 MPa or more and 10 MPa or less, preferably 5 MPa or less.

[denaturation step]
In the modification step, the ring-opening polymer hydrogenated product obtained in the ring-opening polymerization and hydrogenation step is subjected to a modification reaction with a modifying agent to introduce a radical crosslinkable group, thereby forming the structural unit (I) described above. to obtain a cyclic olefin polymer containing

- Denaturant -
The modifier used in the modification reaction can be appropriately selected according to the structure of the desired radical crosslinkable group contained in the structural unit (I). In addition, a modifier|denaturant can be used individually by 1 type or in combination of multiple types.

When introducing a radically crosslinkable group having a styryl skeleton, the modifier may be a functional group (such as a hydroxy group) possessed by the hydrogenated ring-opening polymer and a functional group (halogen group, tosyl group, mesyl group, etc.) capable of undergoing a modification reaction. etc.) and a styryl skeleton (styryl modifier) can be used. Examples of styryl 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, etc. halogenated methylstyrene, 2-(tosylmethyl)styrene, 3-(tosylmethyl)styrene, 4-(tosylmethyl)styrene, 2-(mesylmethyl)styrene, 3-(mesylmethyl)styrene, 4-(mesylmethyl)styrene, etc. . These can be used individually by 1 type or in combination of multiple types. Among these, 4-(chloromethyl)styrene and 4-(bromomethyl)styrene are preferably used from the viewpoint of efficient modification reaction.

When introducing a radical crosslinkable group having an acrylate skeleton, the modifying agent includes a functional group (such as a hydroxy group) possessed by the hydrogenated ring-opening polymer and a functional group capable of modification reaction (halogen group, carboxylic anhydride group etc.) and an acrylate skeleton (acrylate modifier) can be used. Acrylate-based modifiers include acrylic acid chloride, acrylic anhydride, methacrylic acid chloride, and methacrylic acid anhydride. These can be used individually by 1 type or in combination of multiple types. Among these, it is preferable to use acrylic acid chloride and methacrylic acid chloride from the viewpoint of efficiently performing the modification reaction.

-Procedure and conditions for denaturation reaction-
The procedure and conditions of the modification reaction are not particularly limited, and can be appropriately set, for example, according to the type of modifier used. The reaction solvent in the modification reaction is not particularly limited, and for example, the same reaction solvent as used in the ring-opening polymerization reaction can be used.

For example, when a styryl-based modifier is used as the modifier, the modification reaction can be carried out, for example, by reacting the hydrogenated ring-opening polymer with the styryl-based modifier in the presence of a base in a reaction solvent. At that time, the base is not particularly limited, and alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, and t-butoxylithium. , t-butoxysodium, t-butoxypotassium metal alkoxides, triethylamine, pyridine, diazabicycloundecene, diazabicyclononene, tetramethylguanidine, and the like can be used. Among these, metal alkoxides such as t-butoxylithium, t-butoxysodium, and t-butoxypotassium are preferably used from the viewpoint of efficient modification reaction.
When a styryl-based modifier is used as the modifier, it is preferable to use a compound capable of generating iodide ions, such as potassium iodide and tetrabutylammonium iodide, as a catalyst. By blending such a catalyst, the reaction in the modification step can be promoted. The blending ratio of the catalyst capable of generating iodide ions may be, for example, 1.0 parts by mass or more and 10.0 parts by mass or less per 100 parts by mass of the hydrogenated ring-opening polymer.
When a styryl-based modifier is used as the modifier, the modification reaction temperature and modification reaction time are not particularly limited, but the modification reaction temperature is usually −10° C. or more and 100° C. or less, and the modification reaction time is usually 1 hours or more and 15 hours or less.

Further, for example, when an acrylate-based modifier is used as the modifier, the modification reaction can be carried out by reacting the hydrogenated ring-opening polymer with the acrylate modifier in the presence of a modification reaction catalyst in a reaction solvent. . At that time, the modification reaction catalyst is not particularly limited, and for example, triethylamine, pyridine, or the like can be used. When an acrylate-based modifier is used as the modifier, the modification reaction temperature and modification reaction time are not particularly limited, but the modification reaction temperature is usually −10° C. or higher and 15° C. or lower, and the modification reaction time is usually , from 1 hour to 15 hours.

<Radical initiator>
The radical initiator is a component capable of cross-linking the cyclic olefin polymer by generating radicals by exposure or heating to react radical cross-linkable groups when obtaining a resin film using the resin composition.
Here, as the radical initiator, for example, a photo-radical generator, a thermal radical generator, or the like can be used. In addition, a radical initiator can be used individually by 1 type or in combination of multiple types. As the radical initiator, it is preferable to use a photoradical generator.

<<Photo radical generator>>
Acylphosphine oxide-based, oxime ester-based, or aromatic ketone-based photo-radical generators can be used as the photo-radical generator. A photoradical generator can be used individually by 1 type or in combination of multiple types. Among them, it is preferable to use an oxime ester-based photo-radical generator as the photo-radical generator from the viewpoint of improving the exposure sensitivity and the residual film rate after development.

Acylphosphine oxide photoradical generators include, for example, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 2,4,6- Trimethylbenzoylphenylethoxyphosphine oxide and the like can be used.

Examples of oxime ester photoradical generators include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(o-benzoyloxime) (manufactured by BASF, "Irgacure (registered trademark) OXE01"); ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (manufactured by BASF, "Irgacure OXE02 ”); and a compound (chemical formula unpublished) manufactured by BASF and distributed as “Irgacure OXE03”.

As aromatic ketone photoradical generators, benzophenone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-hydroxycyclohexylphenyl Ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1, 2-hydroxy-2-methyl-1 -phenyl-propan-1-one, 2-methyl-1[4-methylthio]phenyl]-2-morpholinopropan-1-one, methyl o-benzoylbenzoate, [4-(methylphenylthio)phenyl]phenyl Methane, 1,4 dibenzoylbenzene, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoyldiphenyl ether, benzyl and the like can be used.

<<Content of radical initiator>>
The content of the radical initiator in the resin composition of the present invention is preferably 0.3 parts by mass or more, more preferably 1 part by mass or more, per 100 parts by mass of the cyclic olefin polymer. It is more preferably at least 25 parts by mass, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less. If the content of the radical initiator in the resin composition is 0.3 parts by mass or more per 100 parts by mass of the cyclic olefin polymer, the resin film formed from the resin composition is formed using a cyclic ketone as the developer. patterning properties can be sufficiently improved. On the other hand, if the content of the radical initiator in the resin composition is 25 parts by mass or less per 100 parts by mass of the cyclic olefin polymer, the value of the dielectric loss tangent of the resin film formed from the resin composition can be reduced. .

<Crosslinking agent having at least two polymerizable unsaturated bonds>
The resin composition of the present invention preferably contains a cross-linking agent having at least two polymerizable unsaturated bonds from the viewpoint of reducing the dielectric loss tangent of the resin film to be obtained and improving the extensibility.
Here, when a resin film is obtained using the resin composition, the cross-linking agent reacts with the cyclic olefin polymer through a radical reaction initiated by the above-described radical initiator, and cooperates with the cyclic olefin polymer in the resin film. It is a component that can form a strong crosslinked structure.

The cross-linking agent is not particularly limited as long as it has two or more polymerizable unsaturated bonds, and any cross-linking agent can be used. In addition, a crosslinking agent can be used individually by 1 type or in combination of multiple types.
Examples of the cross-linking agent include a (meth)acryloyl group-containing cross-linking agent, a styryl group-containing cross-linking agent, and an allyl group-containing cross-linking agent.
In addition, in this specification, "(meth)acryloyl" means acryloyl and/or methacryloyl.
Cross-linking agents having a (meth)acryloyl group include 1,6-hexanediol dimethacrylate, trimethylolprohane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, tris(2-acryloyloxyethyl) isocyanurate, and bisphenol. A dimethacrylate, polybutadiene-terminated diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., "BAC-45"), polyphenylene ether having a methacryloyl group (manufactured by SABIC, "Noryl (registered trademark) SA9000"), and the like.
Cross-linking agents having a styryl group include 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene, and 1,4-diisopropenylbenzene "OPE-2St 1200" and "OPE- 2St 2200" (all manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like.
Examples of crosslinking agents having an allyl group include diallyl ether, tetraallyloxyethane, pentaerythritol triallyl ether, 9,9-bis(4-allyloxyphenyl)fluorene, diallyl adipate, and 1,3,5-benzenetricarboxylic acid. triallyl, triallyl cyanurate, diallylpropyl isocyanurate, triallyl isocyanurate (crosslinking agent (III), hereinafter sometimes abbreviated as "TAIC"), 2,4,6-trimethyl-2,4,6- and trivinylcyclotrisiloxane.

Then, as the cross-linking agent, from the viewpoint of further improving the extensibility while further reducing the dielectric loss tangent of the resin film formed from the resin composition, the cross-linking agent (III) represented by the following formula (III) and the following formula A cross-linking agent (IV) represented by (IV) is preferred.

In crosslinker (IV), A is a divalent organic group. Here, as the divalent organic group constituting A in formula (IV), an organic group represented by the following formula (VII) is preferable.

In formula (VII), R ^a , R ^b , R ^c , R ^d , R ^e , R ^f , R ^g and R ^h each independently represent a hydrogen atom, a halogen atom, or an alkyl having 1 to 6 carbon atoms or a phenyl group.
Halogen atoms that can be R ^a to R ^h in formula (VII) include, for example, fluorine, chlorine, bromine and iodine atoms.
The alkyl group having 1 to 6 carbon atoms that can be R ^a to R ^h in formula (II) is not particularly limited, but is preferably a methyl group or an ethyl group, more preferably a methyl group.

In the cross-linking agent (IV), a and b are each independently an integer of 0 or more and 300 or less. However, the case where one of a and b is 0 is excluded. From the viewpoint of further reducing the dielectric loss tangent of the resin film formed from the resin composition and further improving the stretchability, each of a and b is preferably an integer of 1 or more and 100 or less, and 1 or more and 50 or less. An integer is more preferable, and an integer of 1 or more and 10 or less is even more preferable.

The number average molecular weight of the cross-linking agent (IV) is preferably 100 or more, preferably 300 or more, from the viewpoint of further improving the extensibility while further reducing the dielectric loss tangent of the resin film formed from the resin composition. more preferably 500 or more, particularly preferably 1,000 or more, preferably 3,000 or less, and more preferably 2,500 or less.

<<Content of cross-linking agent>>
The content of the cross-linking agent in the resin composition of the present invention is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and 20 parts by mass or more per 100 parts by mass of the cyclic olefin polymer. more preferably 25 parts by mass or more, particularly preferably 30 parts by mass or more, preferably 100 parts by mass or less, more preferably 90 parts by mass or less, It is more preferably 80 parts by mass or less, and particularly preferably 70 parts by mass or less. If the content of the cross-linking agent in the resin composition is 5 parts by mass or more per 100 parts by mass of the cyclic olefin polymer, the dielectric loss tangent of the resin film formed from the resin composition can be reduced while the extensibility can be improved. can. On the other hand, if the content of the cross-linking agent in the resin composition is 100 parts by mass or less per 100 parts by mass of the cyclic olefin polymer, the resin film formed from the resin composition can be formed using a cyclic ketone as the developer. Sufficient patterning characteristics can be ensured.

<<Combination of cross-linking agent>>
Moreover, from the viewpoint of improving extensibility while reducing the dielectric loss tangent of the resin film formed from the resin composition, the resin composition preferably contains both the cross-linking agent (III) and the cross-linking agent (IV).
And when the resin composition contains both the cross-linking agent (III) and the cross-linking agent (IV), the content of the cross-linking agent (III) in the resin composition is equal to the content of the cross-linking agent (III) and the cross-linking agent (IV) Assuming that the total content of the is preferred, 50% by mass or less is more preferred, and 40% by mass or less is even more preferred. If the ratio of the content of the cross-linking agent (III) to the total content of the cross-linking agent (III) and the cross-linking agent (IV) is within the above range, the dielectric loss tangent of the resin film formed from the resin composition is reduced. while improving extensibility.

<Solvent>
The solvent that the resin composition of the present invention may optionally contain is not particularly limited. Aromatic solvents such as 5-trimethylbenzene and tetralin, hydrocarbon solvents such as cyclohexane and decalin, ether solvents such as dibutyl ether, diisoamyl ether, tetrahydrofuran, cyclopentyl methyl ether, and anisole, butyl acetate, hexyl acetate, Ester solvents such as propylene glycol monomethyl ether acetate, and ketone solvents such as methyl ethyl ketone, diisobutyl ketone, and cyclopentanone are included. These solvents can be used singly or in combination.

The content of the solvent in the resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, and preferably 60% by mass, based on the total mass of the resin composition other than the solvent. Hereinafter, it is preferable to set the amount to be 50% by mass or less, more preferably.

<Additional ingredients>
Moreover, the additive component that the resin composition of the present invention may optionally contain is not particularly limited, and examples thereof include surfactants, antioxidants, sensitizers, adhesion aids, and the like. These additive components can be used individually by 1 type or in combination of multiple types. Above all, from the viewpoint of improving the coatability of the resin composition of the present invention and improving the uniformity of the film thickness of the resulting resin film, it is preferable to contain a surfactant as an additive component.

The surfactant is not particularly limited, and known silicone-based surfactants, fluorine-based surfactants, and the like can be used. The content of the surfactant in the resin composition is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, relative to the total mass of the resin composition.

<Method for preparing resin composition>
The resin composition of the present invention can be prepared by mixing the essential components and various optional components described above by known methods. Here, the resin composition of the present invention is used, for example, as a resin composition obtained by dissolving each component in a solvent and filtering. For dissolution in a solvent, known mixers such as stirrers, ball mills, sand mills, bead mills, pigment dispersers, crushers, ultrasonic dispersers, homogenizers, planetary mixers and Filmix can be used. Moreover, at the time of filtration, a general filtration method using a filter medium such as a filter can be employed.

<Method for producing resin film>
The resin composition of the present invention can form a resin film by using a known film forming method (see, for example, International Publication No. 2015/033901). Then, the obtained resin film is not particularly limited, and an exposure step of irradiating an arbitrary active energy ray, for example, exposure light with a wavelength of 200 nm or more and 500 nm or less, and a development step. It is possible to form a resin film having a pattern of
In particular, the resin film formed from the resin composition of the present invention can efficiently form a desired pattern shape even when a cyclic ketone such as cyclopentanone or cyclohexanone is used as a developer in the development process. can.
If necessary, a pre-baking process may be performed prior to the exposure process, or a post-exposure bake (PEB) process may be performed at a desired timing after the start of the exposure process. Furthermore, if necessary, a post-baking process may be performed after the development process is completed.

EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited to these examples. In the following description, "%" and "parts" representing amounts are based on mass unless otherwise specified.
In Examples and Comparative Examples, measurements of various attributes and various evaluations were carried out by the following methods.

<Weight average molecular weight and molecular weight distribution>
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the cyclic olefin polymers obtained in Examples and Comparative Examples were measured using gel permeation chromatography, and the molecular weight distribution (Mw/Mn) was calculated.
Specifically, using a gel permeation chromatograph (manufactured by Tosoh, HLC-8220), using tetrahydrofuran as a developing solvent, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the cyclic olefin polymer were measured using standard polystyrene. It was obtained as a converted value. Then, the molecular weight distribution (Mw/Mn) was calculated.
<Extensibility (tensile elongation) and mechanical strength (tensile strength)>
Resin composition prepared in each example and each comparative example on a 4-inch silicon wafer on which an aluminum film with a thickness of 50 nm was formed using a sputtering device ("i-Miller CFS-4EP-LL" manufactured by Shibaura Eletech) After the product was spin-coated, it was pre-baked at 90° C. for 2 minutes using a hot plate to form a resin film made of the resin composition. After performing exposure of 1,000 mJ/cm ² using a mask aligner, the resin film was cured by heating at 230° C. for 1 hour in nitrogen to obtain a silicon wafer with a resin film having a thickness of 10 μm. The obtained silicon wafer with a resin film was immersed in a 0.1 mol % hydrochloric acid aqueous solution for 12 hours to etch aluminum, thereby peeling off the resin film from the wafer with a resin film. dried for an hour.
A test piece having a width of 5 mm and a length of 40 mm was cut from the dried resin film, and a tensile test was performed on the test piece. Specifically, a tensile test was performed using a tensile tester ("AGS-10kNX" manufactured by Shimadzu Corporation) at 23°C at a grip interval of 20 mm and a tensile speed of 2 mm/min, and the elongation and strength at the breaking point were measured. bottom. Eight test pieces were tested, and the average value of the top three points was used as the tensile elongation rate and tensile strength of the resin film formed using the resin composition obtained in each example and each comparative example, according to the following criteria. evaluated. It means that the larger the value of the tensile elongation, the higher the extensibility of the resin film. Further, the higher the extensibility of the resin film, the less likely cracks or peeling will occur during the temperature cycle test or the drop impact test, which is preferable. Moreover, it means that the higher the tensile strength, the higher the mechanical strength of the resin film.
<<Extensibility>>
A: Tensile elongation is 10% or more B: Tensile elongation is 5% or more and less than 10% C: Tensile elongation is less than 5% <<Mechanical strength>>
A: Tensile strength of 70 MPa or more B: Tensile strength of 60 MPa or more and less than 70 MPa C: Tensile strength of less than 60 MPa <dielectric loss tangent>
Resin composition prepared in each example and each comparative example on a 4-inch silicon wafer on which an aluminum film with a thickness of 50 nm was formed using a sputtering device ("i-Miller CFS-4EP-LL" manufactured by Shibaura Eletech) After the product was spin-coated, it was pre-baked at 90° C. for 2 minutes using a hot plate to form a resin film made of the resin composition. Then, after exposure with a mask aligner ("PLA501F" manufactured by Canon Inc.) using a ghi mixed beam at a dose of 1000 mJ/ ^cm2 , the resin film was cured by heating at 180°C for 1 hour in nitrogen. Thus, a silicon wafer with a resin film having a thickness of 10 μm was obtained. The obtained silicon wafer with a resin film was immersed in a 0.1 mol % hydrochloric acid aqueous solution for 12 hours to etch aluminum, thereby peeling off the resin film from the silicon wafer. After drying in an oven at 110° C. for 1 hour, a strip of 2 mm in width and 50 mm in length was cut into a test piece, and the dielectric loss tangent of this test piece was measured at 10 GHz by the cavity resonator method.
A: Dielectric loss tangent less than 0.0035 B: Dielectric loss tangent 0.0035 or more and less than 0.0040 C: Dielectric loss tangent 0.0040 or more <Presence or absence of turbidity>
After spin-coating the resin composition prepared in each example and each comparative example on an inch silicon wafer, it was pre-baked at 90° C. for 2 minutes using a hot plate to form a resin film made of the resin composition. The obtained resin film was visually observed to confirm the presence or absence of turbidity.
<Patterning characteristics>
After spin-coating the resin composition prepared in each example and each comparative example on an inch silicon wafer, it was pre-baked at 90° C. for 2 minutes using a hot plate to form a resin film made of the resin composition. Then, using a mask aligner (manufactured by Canon, "PLA501F"), using ghi mixed rays, exposure was performed at a dose of 700 mJ/cm ² through a mask having a hole pattern with a diameter of 100 μm. Development was performed by immersion for 90 seconds. The presence or absence of hole pattern openings on the resin film after development was confirmed using an optical microscope.

(Example 1)
<Synthesis of Cyclic Olefin Polymer (B-1)>
<<Ring-opening polymerization and hydrogenation step>>
2-norbornene-5-methanol (hereinafter abbreviated as "NBMOH") as a norbornene-based monomer (I) 15 mol% and methanotetrahydrofluorene as a norbornene-based monomer (II) (hereinafter referred to as " 100 parts of a monomer mixture consisting of 85 mol%, 1.0 parts of 1,5-hexadiene as a molecular weight modifier, and (1,3-dimesitylimidazoline as a ring-opening polymerization catalyst -2-ylidene)(tricyclohexylphosphine)benzylidene ruthenium dichloride] (Org. Lett., Vol. 1, p. 953, synthesized by the method described in 1999) 0.025 parts, and tetrahydrofuran 300 as a reaction solvent The mixture was placed in a nitrogen-purged glass pressure-resistant reactor and reacted at 80° C. for 4 hours while stirring to obtain a polymerization reaction liquid.
The resulting polymerization reaction solution was placed in an autoclave and stirred for 5 hours at 150° C. and a hydrogen pressure of 4 MPa for hydrogenation reaction, after which 300 parts of tetrahydrofuran as a reaction solvent was added to the reaction solution. This was added dropwise to 8000 parts of methanol, and the resulting precipitate was collected by filtration and dried at 50° C. under reduced pressure to obtain a hydrogenated ring-opening polymer (A-1).
<Degeneration step>
A three-necked flask equipped with a stirring blade and a thermometer was purged with nitrogen, and 100 parts of the hydrogenated ring-opening polymer (A-1), 87.4 parts of triethylamine as a modification reaction catalyst, and as a reaction solvent 500 parts of tetrahydrofuran was charged, and the reaction solution was cooled to 0°C in an ice bath. While maintaining the temperature of the reaction solution at 10° C. or lower, 54.2 parts of methacryloyl chloride as a modifier was added dropwise and stirred for 2 hours. Further, the temperature of the reaction solution was raised to room temperature, and stirring was continued for 12 hours. After adding 200 parts of tetrahydrofuran as a reaction solvent to the reaction solution, the reaction solution was cooled to 0°C, and methanol was added in an amount of 50 parts per 100 parts of methacryloyl chloride while maintaining the temperature of the reaction solution at 10°C or less. , 0° C. for 1 hour, warmed to room temperature and stirred for additional 1 hour.
The reaction liquid was added dropwise to 8000 parts of methanol, and the generated precipitate was collected by filtration. The precipitate was washed with methanol three times and then dried under reduced pressure at 50° C. to obtain a cyclic olefin polymer (B-1) which is a modified hydrogenated ring-opening polymer (see the formula below). The weight average molecular weight of the cyclic olefin polymer (B-1) measured by GPC was 20,100, and the molecular weight distribution was 2.13.
According to ¹ H-NMR measurement, the methacryloyl modification rate of the hydrogenated ring-opening polymer (A-1) was 100%, and the methacryloyl-modified NBMOH-derived structural unit in the cyclic olefin polymer (B-1) was The content was confirmed to be 15 mol %.

<Preparation of resin composition>
100 parts of the cyclic olefin polymer (B-1) obtained as described above, 5 parts of "Irgacure OXE01" (manufactured by BASF) as a radical initiator, and the total mass of the resin composition other than the solvent Addition amounts of anisole (solvent) totaling 30% were mixed and dissolved. Next, after adding KP-341 (manufactured by Shin-Etsu Silicone Co., Ltd.) as a surfactant so as to be 0.03% with respect to the total weight of the resin composition, it was filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm. to prepare a resin composition.
And various evaluations were performed according to the above using the obtained resin composition. Table 1 shows the results.

(Example 2)
Resin was prepared in the same manner as in Example 1, except that the cyclic olefin polymer (B-2) prepared as follows was used instead of the cyclic olefin polymer (B-1) in preparing the resin composition. A composition was prepared.
And various evaluations were performed according to the above using the obtained resin composition. Table 1 shows the results.
<Synthesis of Cyclic Olefin Polymer (B-2)>
<<Ring-opening polymerization and hydrogenation step>>
The same operation as in Example 1 was carried out, except that NBMOH was changed to tetracyclododecenemethanol (hereinafter abbreviated as "TCDMOH") and tetrahydrofuran was changed to toluene, to obtain a hydrogenated ring-opening polymer (A-2). got
<<Modification step>>
The ring-opening polymer hydrogenate (A-1) was changed to the ring-opening polymer hydrogenate (A-2), the amount of triethylamine was 83.5 parts, the amount of methacrylic acid chloride was 51.3 parts, and tetrahydrofuran. A cyclic olefin polymer (B-2), which is a modified product of the hydrogenated ring-opening polymer, was obtained in the same manner as in Example 1, except that toluene was used. The weight average molecular weight of the cyclic olefin polymer (B-2) measured by GPC was 22,900, and the molecular weight distribution was 2.03.
According to ¹ H-NMR measurement, the methacryloyl modification rate of the hydrogenated ring-opening polymer (A-2) was 100%, and the methacryloyl-modified TCDMOH-derived structural unit in the cyclic olefin polymer (B-2) was The content was confirmed to be 15 mol %.

(Example 3)
When preparing the resin composition, 25 parts of "OPE-2St 1200" (manufactured by Mitsubishi Gas Chemical Company, number average molecular weight: 1,200, having a structure of the following formula (VIII)) as a cross-linking agent (IV) was added. A cyclic olefin polymer (B-1) and a resin composition were prepared in the same manner as in Example 1 except for the above.
And various evaluations were performed according to the above using the obtained resin composition. Table 1 shows the results.

(Example 4)
In preparing the resin composition, a cyclic olefin polymer (B-3) prepared as follows was used in place of the cyclic olefin polymer (B-1), and "OPE-2St 2200" (manufactured by Mitsubishi Gas Chemical Company, number average molecular weight: 2,200, having the structure of formula (VIII) above) was added in the same manner as in Example 1, except that 50 parts of the resin composition was prepared.
And various evaluations were performed according to the above using the obtained resin composition. Table 1 shows the results.
<Synthesis of Cyclic Olefin Polymer (B-3)>
<<Ring-opening polymerization and hydrogenation step>>
A hydrogenated ring-opening polymer (A-3) was obtained in the same manner as in Example 1, except that the MTF was changed to 55 mol % and 30 mol % of phenylnorbornene was added.
<<Modification step>>
The ring-opening polymer hydrogenate (A-1) was changed to the ring-opening polymer hydrogenate (A-3), the amount of triethylamine was changed to 91.9 parts, and the amount of methacrylic acid chloride was changed to 55.3 parts. A cyclic olefin polymer (B-3), which is a modified product of the hydrogenated ring-opening polymer, was obtained by performing the same operation as in Example 1, except for the above (see the formula below). The cyclic olefin polymer (B-3) had a weight average molecular weight of 16,400 and a molecular weight distribution of 1.59 as measured by GPC.
According to ¹ H-NMR measurement, the methacryloyl modification rate of the hydrogenated ring-opening polymer (A-3) was 100%, and the methacryloyl-modified NBMOH-derived structural unit in the cyclic olefin polymer (B-3) was The content was confirmed to be 15 mol %.

(Example 5)
A cyclic olefin polymer (B-1) and a resin composition were prepared in the same manner as in Example 1, except that 20 parts of the cross-linking agent (III) (manufactured by Shinryo Corporation, TAIC) was added in the preparation of the resin composition. bottom.
And various evaluations were performed according to the above using the obtained resin composition. Table 1 shows the results.

(Example 6)
In the preparation of the resin composition, 10 parts of the cross-linking agent (III) (manufactured by Shinryo Corporation, TAIC), "OPE-2St 1200" (Mitsubishi Gas Chemical Co., Ltd., number average molecular weight: 1,200) as the cross-linking agent (IV) A cyclic olefin polymer (B-2) and a resin composition were prepared in the same manner as in Example 2, except that 25 parts of cycloolefin polymer (B-2) was added.
And various evaluations were performed according to the above using the obtained resin composition. Table 1 shows the results.

(Example 7)
In the preparation of the resin composition, 10 parts of the cross-linking agent (III) (manufactured by Shinryo Corporation, TAIC), "OPE-2St 1200" (Mitsubishi Gas Chemical Co., Ltd., number average molecular weight: 1,200) as the cross-linking agent (IV) A cyclic olefin polymer (B-1) and a resin composition were prepared in the same manner as in Example 1, except that 50 parts of cycloolefin polymer (B-1) was added.
And various evaluations were performed according to the above using the obtained resin composition. Table 1 shows the results.

(Example 8)
In the preparation of the resin composition, 10 parts of the cross-linking agent (III) (manufactured by Shinryo Corporation, TAIC), "OPE-2St 2200" (Mitsubishi Gas Chemical Co., Ltd., number average molecular weight: 2,200) as the cross-linking agent (IV) A cyclic olefin polymer (B-2) and a resin composition were prepared in the same manner as in Example 2, except that 25 parts of cycloolefin polymer (B-2) was added.
And various evaluations were performed according to the above using the obtained resin composition. Table 2 shows the results.

(Example 9)
A resin composition was prepared in the same manner as in Example 6, except that the cyclic olefin polymer (B-4) prepared as follows was used instead of the cyclic olefin polymer (B-2) in preparing the resin composition. prepared the product.
And various evaluations were performed according to the above using the obtained resin composition. Table 2 shows the results.
<Synthesis of cyclic olefin polymer (B-4)>
<<Ring-opening polymerization and hydrogenation step>>
A hydrogenated ring-opening polymer (A-4) was obtained in the same manner as in Example 1, except that NBMOH was changed to 50 mol% and MTF was changed to 50 mol%.
<<Modification step>>
The ring-opening polymer hydrogenate (A-1) was changed to the ring-opening polymer hydrogenate (A-4), the amount of triethylamine was changed to 355.5 parts, and the amount of methacrylic acid chloride was changed to 204.2 parts. A cyclic olefin polymer (B-4), which is a modified product of the hydrogenated ring-opening polymer, was obtained by performing the same operation as in Example 1 except for the above (see the formula below). The cyclic olefin polymer (B-4) had a weight average molecular weight of 22,000 and a molecular weight distribution of 2.14 as measured by GPC.
According to ¹ H-NMR measurement, the methacryloyl modification rate of the hydrogenated ring-opening polymer (A-4) was 100%, and the methacryloyl-modified NBMOH-derived structural unit in the cyclic olefin polymer (B-4) was The content was confirmed to be 50 mol %.

(Comparative example 1)
In preparing the resin composition, a cyclic olefin polymer (B-5) prepared as follows was used in place of the cyclic olefin polymer (B-1), and "OPE-2St 1200" (manufactured by Mitsubishi Gas Chemical Company, number average molecular weight: 1,200, having the structure of formula (VIII) above) was added, and tetralin was used in place of anisole. to prepare a resin composition.
And various evaluations were performed according to the above using the obtained resin composition. Table 2 shows the results.
<Synthesis of Cyclic Olefin Polymer (B-5)>
<<Ring-opening polymerization and hydrogenation step>>
The same operation as in Example 1 was carried out, except that MTF was 55 mol% and ethylidenetetracyclododecene (hereinafter abbreviated as "ETD") was added at 30 mol% to obtain a hydrogenated ring-opening polymer (A -5) was obtained.
<<Modification step>>
The ring-opening polymer hydrogenate (A-1) was changed to the ring-opening polymer hydrogenate (A-5), the amount of triethylamine was changed to 355.5 parts, and the amount of methacrylic acid chloride was changed to 204.2 parts. A cyclic olefin polymer (B-5), which is a modified product of the hydrogenated ring-opening polymer, was obtained by performing the same operation as in Example 1 except for the above (see the formula below). The cyclic olefin polymer (B-5) had a weight average molecular weight of 20,000 and a molecular weight distribution of 1.76 as measured by GPC.
According to ¹ H-NMR measurement, the methacryloyl modification rate of the hydrogenated ring-opening polymer (A-5) was 100%, and the methacryloyl-modified NBMOH-derived structural unit in the cyclic olefin polymer (B-5) was The content was confirmed to be 15 mol %.

(Comparative example 2)
In the preparation of the resin composition, the cyclic olefin polymer (B-6) prepared as follows was used instead of the cyclic olefin polymer (B-1), and tetralin was used instead of anisole. A resin composition was prepared in the same manner as in Example 1.
And various evaluations were performed according to the above using the obtained resin composition. Table 2 shows the results.
<Synthesis of cyclic olefin polymer (B-6)>
<<Ring-opening polymerization and hydrogenation step>>
A hydrogenated ring-opening polymer (A-6) was obtained in the same manner as in Synthesis Example 1, except that MTF was changed to ETD.
<<Modification step>>
The ring-opening polymer hydrogenate (A-1) was changed to the ring-opening polymer hydrogenate (A-6), the amount of triethylamine was changed to 94.5 parts, and the amount of methacrylic acid chloride was changed to 53.8 parts. A cyclic olefin polymer (B-6), which is a modified product of the hydrogenated ring-opening polymer, was obtained by performing the same operation as in Example 1 except for the above (see the formula below). The cyclic olefin polymer (B-6) had a weight average molecular weight of 17,700 and a molecular weight distribution of 2.62 as measured by GPC.
According to ¹ H-NMR measurement, the methacryloyl modification rate of the cyclic olefin polymer (A-6) was 100%, and the content of the methacryloyl-modified NBMOH-derived structural unit in the cyclic olefin polymer (B-6) was It was confirmed to be 15 mol %.

(Comparative Example 3)
In preparing the resin composition, instead of the cyclic olefin polymer (B-1), a cyclic olefin polymer (B-7), which is a modified addition polymer prepared as follows, is used, and anisole is replaced with A resin composition was prepared in the same manner as in Example 1, except that tetralin was used.
And various evaluations were performed according to the above using the obtained resin composition. Table 2 shows the results.
<Synthesis of Cyclic Olefin Polymer (B-7)>
<<Addition polymerization step>>
An addition polymer of norbornene and NBMOH (A-7) was synthesized according to the method described in Macromolecules 29, 2761 (1996), except that the scale was increased 20 times.
<<Modification step>>
The ring-opening polymer hydrogenated product (A-1) was changed to the addition polymer (A-7), the amount of triethylamine was changed to 170.4 parts, and the amount of methacrylic acid chloride was changed to 95.3 parts. A cyclic olefin polymer (B-7), which is a modified addition polymer, was obtained by the same procedure as in Example 1 (see the formula below). The weight average molecular weight of the cyclic olefin polymer (B-7) measured by GPC was 28,100, and the molecular weight distribution was 1.84.
According to ¹ H-NMR measurement, the methacryloyl modification rate of the addition polymer (A-7) was 100%, and the content of the methacryloyl-modified NBMOH-derived structural unit in the cyclic olefin polymer (B-7) was 15. was confirmed to be mol %.

(Comparative Example 4)
A cyclic olefin polymer (B-7) was prepared in the same manner as in Comparative Example 3. Then, in preparing the resin composition, the cyclic olefin polymer (B-7) is used instead of the cyclic olefin polymer (B-1), and "OPE-2St 1200" (Mitsubishi Gas Kagaku Co., Ltd., number average molecular weight: 1,200, having the structure of the above formula (VIII). prepared the product.
And various evaluations were performed according to the above using the obtained resin composition. Table 2 shows the results.

From Tables 1 and 2, Examples 1 to 9 containing a cyclic olefin polymer containing the structural unit (I) and the structural unit (II) and having a total content ratio of 80 mol% or more and a radical initiator It can be seen that the resin composition can form a resin film having excellent patterning properties when a cyclic ketone is used as a developer.

Claims

A resin composition comprising a cyclic olefin polymer and a radical initiator,
The cyclic olefin polymer includes a structural unit (I) represented by the following formula (I) and a structural unit (II) represented by the following formula (II), and all structural units contained in the cyclic olefin polymer is 100 mol%, the sum of the content of the structural unit (I) and the content of the structural unit (II) in the cyclic olefin polymer is 80 mol% or more. .

In formula (I), at least one of R 1 to R 4 is a radical crosslinkable group,
R 1 to R 4 that do not correspond to radical crosslinkable groups are each independently a hydrogen atom, an alkyl group or an aromatic ring group, and two of R 1 to R 4 that do not correspond to radical crosslinkable groups may form a ring,
m is an integer of 0 or more and 4 or less.

In formula (II), at least one of R 5 to R 8 is an aromatic ring group, or two of R 5 to R 8 together form an aromatic ring-containing structure,
R 5 to R 8 which do not correspond to an aromatic ring group and do not form an aromatic ring-containing structure are each independently a hydrogen atom or an alkyl group,
n is an integer of 0 or more and 4 or less.
2. The method according to claim 1, wherein the content of the structural unit (II) in the cyclic olefin polymer is 70 mol% or more when the amount of all structural units contained in the cyclic olefin polymer is 100 mol%. The described resin composition.
The resin composition according to claim 1, wherein the radical crosslinkable group has at least one of a styryl skeleton and an acrylate skeleton.
The resin composition according to any one of claims 1 to 3, further comprising a cross-linking agent having at least two polymerizable unsaturated bonds.
The resin composition according to claim 4, wherein the cross-linking agent contains at least one of a cross-linking agent (III) represented by the following formula (III) and a cross-linking agent (IV) represented by the following formula (IV).

In formula (IV), A is a divalent organic group, and a and b are integers of 0 or more and 300 or less. Note that a and b may be the same or different, except when only one of a and b is 0.