Polynorbornene-containing solution, polynorbornene powder, photosensitive resin composition, and semiconductor device.

Abstract

This invention provides a method for producing polynorbornene that has a low weight-average molecular weight and excellent compatibility with other materials, while also offering high yield and excellent safety. [Solution] The present invention provides a method for producing polynorbornene, comprising the step of polymerizing a norbornene-based compound in a solvent in the presence of a palladium catalyst and a chain transfer agent, wherein the solvent does not contain toluene and trifluorotoluene or is below the detection limit in GC / MS measurement, and the difference between the Hansen solubility parameter a of the polynorbornene and the Hansen solubility parameter b of the solvent is 8 or less.

Description

[Technical Field]

[0001] The present invention relates to a method for producing polynorbornene, a polynorbornene-containing solution, polynorbornene powder, a photosensitive resin composition, and a semiconductor device. [Background technology]

[0002] Norbornene-based resins have traditionally been used in various applications as molded products due to their excellent electrical properties, optical properties, and low hygroscopicity.

[0003] Patent Document 1 discloses norbornene-based polymers or polymer compositions containing norbornene-based polymers. Specifically, it describes an example of homopolymerization of 1-[4-(5-2-norbornyl)butyl]-3,4-dimethylpyrrole-2,5-dione (NBBuDMMI) in toluene (paragraphs 0173 and 0176).

[0004] Patent Document 2 discloses a block copolymer having a predetermined structure. Specifically, it describes an example of homopolymerization of NBBuDMMI in trifluorotoluene in the presence of a predetermined palladium catalyst, in which the synthesis is carried out using 1 mole of the predetermined palladium catalyst per 100 moles of NBBuDMMI (paragraphs 0251, 0253).

[0005] Furthermore, polyimide resins possess high mechanical strength, heat resistance, insulation, and solvent resistance, making them widely used as thin films for electronic materials such as protective materials, insulating materials, and color filters in liquid crystal display elements and semiconductors. Patent Document 3 discloses a photosensitive composition containing a polyimide having a predetermined maleimide group at its terminus. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Special Publication No. 2013-541191 [Patent Document 2] Special Publication No. 2017-525808 [Patent Document 3] International Publication No. 2020 / 181021 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] However, in the conventional manufacturing method described in Patent Document 1, the weight-average molecular weight of the resulting polymer was large, leaving room for improvement in its compatibility with other materials. Furthermore, the reaction was carried out in toluene, and toluene remained in the resulting polymer, posing a safety problem.

[0008] In the conventional manufacturing method described in Patent Document 2, although the weight-average molecular weight of the obtained polymer is small, the conversion rate is low despite the long reaction time (20 hours), and there is room for improvement in the polymer yield. Furthermore, since the reaction is carried out in trifluorotoluene, trifluorotoluene remains in the obtained polymer, which poses a safety problem. [Means for solving the problem]

[0009] The inventors of the present invention have found that the above problems can be solved by polymerizing norbornene compounds in a predetermined solvent other than toluene and trifluorotoluene, in the presence of a palladium catalyst and a chain transfer agent, and have completed the present invention. In other words, the present invention can be described as follows.

[0010] According to the present invention, The process includes polymerizing a norbornene-based compound in a solvent in the presence of a palladium catalyst and a chain transfer agent to obtain polynorbornene. The aforementioned solvent does not contain toluene and trifluorotoluene, or its levels are below the detection limit in GC / MS measurements. A method for producing polynorbornene is provided, wherein the difference between the Hansen solubility parameter a of the polynorbornene and the Hansen solubility parameter b of the solvent is 8 or less.

[0011] According to the present invention, A polynorbornene-containing solution is provided, which contains polynorbornene with a structural unit represented by the following general formula (1a), and is free of toluene and trifluorotoluene or has levels below the detection limit in GC / MS measurement. [ka] (In general formula (1a), R 1 and R 2 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q 1 This indicates a single bond or a divalent organic group, G 1 , G 2 , and G 3 Each of these independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group with 1 to 30 carbon atoms, and m is 0, 1, or 2.

[0012] According to the present invention, A polynorbornene powder containing the structural unit represented by the general formula (1a) is provided, which is free of toluene and trifluorotoluene or is below the detection limit in GC / MS measurement.

[0013] According to the present invention, A photosensitive resin composition is provided, comprising the aforementioned polynorbornene powder and polyimide.

[0014] According to the present invention, A cured film is provided, which is made from a cured product of the aforementioned photosensitive resin composition.

[0015] According to the present invention, A semiconductor device is provided that comprises a resin film containing a cured product of the aforementioned photosensitive resin composition. [Effects of the Invention]

[0016] According to the present invention, it is possible to obtain polynorbornene with a low weight-average molecular weight and excellent compatibility with other materials, as well as a method for producing polynorbornene with high yield and excellent safety. Furthermore, according to the present invention, it is possible to provide polynorbornene that does not contain toluene or trifluorotoluene or is below the detection limit in GC / MS measurement, thus providing excellent safety. Moreover, according to the present invention, because polynorbornene has excellent compatibility with other materials, it is possible to provide a photosensitive resin composition containing polynorbornene and polyimide. [Brief explanation of the drawing]

[0017] [Figure 1] This is a schematic cross-sectional view of the semiconductor device according to this embodiment. [Modes for carrying out the invention]

[0018] Embodiments of the present invention will be described below with reference to the drawings. In all drawings, similar components are denoted by the same reference numerals, and their descriptions are omitted as appropriate. Also, for example, "1 to 10" represents "1 or more" to "10 or less" unless otherwise specified.

[0019] The method for producing polynorbornene according to this embodiment includes the step of polymerizing a norbornene-based compound in a solvent in the presence of a palladium catalyst and a chain transfer agent. In this embodiment, for example, solution polymerization can be performed by dissolving a norbornene compound, a palladium catalyst, and a chain transfer agent in a solvent, and then heating them for a predetermined time. In this case, the heating temperature can be, for example, 30°C to 120°C, preferably 40°C to 100°C, and more preferably 50°C to 80°C.

[0020] Furthermore, the heating time can be, for example, 0.5 to 10 hours. It is more preferable to remove moisture from the reaction system by nitrogen aeration before performing solution polymerization.

[0021] (Norbornene compounds) As the norbornene-based compound of the present embodiment, a norbornene-based compound known within the scope where the effects of the present invention are exhibited can be used, but it preferably includes a compound represented by the following general formula (1).

[0022]

Chemical formula

[0023] In general formula (1), R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and at least one of them is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably both are alkyl groups having 1 to 3 carbon atoms. From the viewpoint of the effects of the present invention, the alkyl group having 1 to 3 carbon atoms is preferably an alkyl group having 1 or 2 carbon atoms, and more preferably an alkyl group having 1 carbon atom.

[0024] Q 1 represents a single bond or a divalent organic group. As the divalent organic group, an organic group known within the scope where the effects of the present invention are exhibited can be used, and examples thereof include an alkylene group having 1 to 8 carbon atoms or a (poly)alkylene glycol chain. The alkylene group having 1 to 8 carbon atoms is preferably an alkylene group having 2 to 6 carbon atoms.

[0025] Examples of the alkylene group having 1 to 8 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, and an octylene group.

[0026] The alkylene oxides constituting the (poly)alkylene glycol chain are not particularly limited, but are preferably composed of alkylene oxides having 1 to 18 carbon atoms, and more preferably alkylene oxides having 2 to 8 carbon atoms. Examples include ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, trimethylethylene oxide, tetramethylene oxide, tetramethylethylene oxide, butadiene monooxide, octylene oxide, and the like.

[0027] G 1 , G 2 , and G 3 Each of these independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, or a hydrogen atom.

[0028] Examples of hydrocarbon groups having 1 to 30 carbon atoms include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkalil groups, or cycloalkyl groups.

[0029] Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. Examples of alkenyl groups include allyl, pentenyl, and vinyl groups. An example of an alkynyl group is the ethynyl group. Examples of alkylidene groups include the methylidene group and the ethylidene group.

[0030] Examples of aryl groups include phenyl, naphthyl, and anthracenyl groups. Examples of aralkyl groups include benzyl and phenethyl groups.

[0031] Examples of alkaryl groups include tolyl and xylyl groups. Examples of cycloalkyl groups include adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. A hydrocarbon group having 1 to 30 carbon atoms may contain at least one atom selected from O, N, S, P, and Si in its structure.

[0032] In this embodiment, the hydrocarbon group having 1 to 30 carbon atoms is preferably a hydrocarbon group having 1 to 15 carbon atoms, and more preferably a hydrocarbon group having 1 to 10 carbon atoms. Furthermore, the hydrocarbon group having 1 to 30 carbon atoms is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and even more preferably an alkyl group having 1 to 10 carbon atoms.

[0033] Substituents of C1-C30 hydrocarbon groups can include hydroxyl groups, amino groups, cyano groups, ester groups, ether groups, amide groups, sulfonamide groups, etc., and may be substituted with at least one of these groups.

[0034] In this embodiment, G 1 , G 2 , and G 3 Preferably, one of them is a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, and the rest are hydrogen atoms; more preferably, all are hydrogen atoms. m is 0, 1, or 2, preferably 0 or 1, and more preferably 0.

[0035] The polynorbornene of this embodiment has excellent low dielectric loss tangent because it possesses structural units derived from the compound of general formula (1). Furthermore, since the polynorbornene has a predetermined maleimide group in its side chain, photodimerization is possible without radical reactions, allowing for photopolymerization of polynorbornene molecules, resulting in superior mechanical strength.

[0036] (solvent) The solvent used in the polymerization reaction of this embodiment does not contain toluene or trifluorotoluene. Furthermore, in this embodiment, a solvent is used in which the difference (Hansen distance Ra) between the Hansen solubility parameter a of the obtained polynorbornene and the Hansen solubility parameter b of the solvent is 8 or less, preferably 7 or less, and more preferably 6 or less.

[0037] In this embodiment, the Hansen solubility parameter a of polynorbornene is measured by the following method. [method] In a 5 ml glass container, add 1 ml of any solvent selected from the evaluation solvents listed below to 0.05 g of polynorbornene, and after stirring with a mixing rotor for 1 hour, visually evaluate the dispersibility in the following three stages. Input all evaluation solvents and the evaluation results for dispersibility in each solvent into the Sphere program of the computer software HSPiP (version 5.2.02) and calculate the Hansen solubility parameter. (Solvent for evaluation) Hexane, cyclohexane, toluene, benzyl benzoate, propylene carbonate, 1-hexene, methyl ethyl ketone, acetone, acetonitrile, ethyl acetate, propylene glycol monomethyl ether acetate, cyclohexanol, isopropyl alcohol, methanol (evaluation) 1: Dissolve completely. 2: It partially dissolves. 6: Does not dissolve.

[0038] By using a solvent in which the Hansen distance to polynorbornene is within a predetermined range, the synthesis reaction proceeds smoothly due to the excellent solubility of polynorbornene, even without using toluene and trifluorotoluene, and the yield is improved due to the excellent conversion rate. Furthermore, since polynorbornene powder is obtained, it has excellent handling properties.

[0039] The Hansen solubility parameter is an index of solubility that indicates how much of one substance dissolves in another. The Hansen solubility parameter can represent solubility as a three-dimensional vector, specifically the dispersion term (δ D ), polarization term (δ P ), hydrogen bond term (δ H It can be represented as ).

[0040] In this embodiment, the Hansen distance Ra is defined by the dispersion term (δ D ), polarization term (δ P ), hydrogen bond term (δ H This is the distance between polynorbornene (A) and solvent (B) in a three-dimensional space with coordinates ), and can be calculated specifically using the following formula. Formula: Ra=[4(δ DA -δ DB ) 2 +( δ PA -δ PB ) 2 +( δ HA -δ HB ) 2 ] 1 / 2

[0041] The smaller the value of the Hansen distance Ra, the better the compatibility between polynorbornene (A) and the solvent (B), and it is preferable that the Hansen distance Ra is within the above range.

[0042] The solvent may be a single solvent or a mixture of two or more solvents. The solvent is not particularly limited as long as it satisfies the above range of Hansen distance Ra, but from the viewpoint of the effects of the present invention, it is preferable to include at least one selected from ether-based solvents and hydrocarbon-based solvents that do not contain aromatic rings.

[0043] As the ether-based solvent, any solvent known within the range that exhibits the effects of the present invention can be used, and preferably, it contains at least one selected from, for example, cyclopentyl methyl ether and methyltetrahydropyran. By including these solvents, powdered polynorbornene can be suitably obtained in the reprecipitation step described later.

[0044] As the hydrocarbon solvent that does not contain an aromatic ring, any solvent known within the range that exhibits the effects of the present invention can be used, and it is preferable that it includes, for example, at least one selected from cyclohexane and methylcyclohexane.

[0045] The solvent is more preferably a mixed solvent of ethyl acetate and at least one selected from cyclopentyl methyl ether, methyltetrahydropyran, cyclohexane, and methylcyclohexane.

[0046] When the solvent is a mixture of two or more solvents, it is preferable that the difference (Hansen distance Ra) between the Hansen solubility parameter a of polynorbornene and the Hansen solubility parameter c of the mixture of two or more solvents is within the above range.

[0047] (Palladium catalyst) The palladium catalyst mentioned above is not particularly selected as long as addition polymerization proceeds, but for example, a phosphine-based or diimine-based ligand may be coordinated to the palladium complex, and a counteranion may also be used. One or more of these can be used.

[0048] Examples of the above palladium complexes include (acetato-κ0)(acetonitrile)bis[tris(1-methylethyl)phosphine]palladium(I)tetrakis(2,3,4,5,6-pentafluorophenyl)borate, π-allylpalladium chloride dimer, and other allylpalladium complexes. Palladium organic carboxylates such as palladium acetate, propionate, maleate, and naphthoate, Palladium organic carboxylic acid complexes such as palladium acetate triphenylphosphine complex, palladium acetate tri(m-tolyl)phosphine complex, and palladium acetate tricyclohexylphosphine complex. Palladium dibutyl phosphate, p-toluenesulfonate and other palladium organosulfonates, Palladium β-diketone compounds such as bis(acetylacetonate)palladium, bis(hexafluoroacetylacetonate)palladium, bis(ethylacetoacetate)palladium, and bis(phenylacetoacetate)palladium. Examples include palladium halide complexes such as dichlorobis(triphenylphosphine)palladium, bis[tri(m-tolylphosphine)]palladium, dibromobis[tri(m-tolylphosphine)]palladium, and acetonyltriphenylphosphine complexes.

[0049] Examples of the phosphine ligands mentioned above include triphenylphosphine, dicyclohexylphenylphosphine, cyclohexyldiphenylphosphine, and tricyclohexylphosphine.

[0050] Examples of the above counteranions include triphenylcarbenium tetrakis(pentafluorophenyl) borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl] borate, triphenylcarbenium tetrakis(2,4,6-trifluorophenyl) borate, triphenylcarbenium tetraphenyl borate, tributylammonium tetrakis(pentafluorophenyl) borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, N,N-diethylanilinium tetrakis(pentafluorophenyl) borate, N,N-diphenylanilinium tetrakis(pentafluorophenyl) borate, and lithium tetrakis(pentafluorophenyl) borate.

[0051] The amount of palladium catalyst can be 1 / 20,000 mole to 1 / 500 mole per mole of the norbornene compound, preferably 1 / 10,000 mole to 1 / 1,000 mole, and more preferably 1 / 5,000 mole to 1 / 2,000 mole. This can further improve the yield of polynorbornene.

[0052] In this embodiment, since a norbornene compound and a predetermined solvent are used, the amount of palladium catalyst used in the reaction is reduced, and the amount of residual palladium contained in the resulting polynorbornene can be reduced, resulting in polynorbornene having excellent dielectric properties such as dielectric loss tangent.

[0053] (Chain transfer agent) In this embodiment, the chain transfer agent can be any known chain transfer agent within the range that provides the effects of the present invention, but it is preferable that it contains at least one selected from the compound represented by the following general formula (a), formic acid, and oxalic acid. By using a chain transfer agent, the amount of palladium catalyst can be reduced, and polynorbornene with a lower weight-average molecular weight can be obtained.

[0054] [ka]

[0055] In general formula (a), R 1 , R 2 and R 3 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. Examples of compounds represented by general formula (a) include trimethylsilane, triethylsilane, and tributylsilane.

[0056] The chain transfer agent can be used in an amount of preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, per 100 parts by mass of the norbornene compound.

[0057] (Other ingredients) In addition, molecular weight regulators, co-catalysts, etc., may be added to the reaction as needed.

[0058] It is preferable to include an ionic complex containing a weakly coordinating anionic salt as a co-catalyst. That is, when synthesizing the addition-type norbornene resin, it is preferable to add a co-catalyst in addition to the catalyst. This makes it possible to further increase the polymerization rate of the addition-type norbornene monomer.

[0059] The aforementioned co-catalysts are not particularly limited, but examples include alkylaluminum, Lewis acids, or ionic complexes containing weakly coordinating anions (WCA) salts, and among these, ionic complexes containing weakly coordinating anions (WCA) salts are preferred.

[0060] Furthermore, the co-catalyst is more preferably one represented by the following formula (i). [C] e [WCA] d Equation (i) (In the above formula, C is a proton (H + ), represents an organic group-containing cation, or an alkali metal, alkaline earth metal, or transition metal cation. WCA is defined as described above, and e and d are numbers determined to balance the electron charges on the combined salt complex of the cation complex (C) and the weakly coordinating anionic salt (WCA), respectively.

[0061] The ionic complex containing the weakly coordinating anion (WCA) salt is not particularly limited, but may include lithium (diethyl ether). 2.5 Tetrakis(pentafluorophenyl)borate, dimethylanilinium-tetrakis(pentafluorophenyl)borate, dimethylanilinium-tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, H(OEt2) xExamples include tetrakis(pentafluorophenyl)borate, tetrakis[(4-methyl)-α,α-bis(trifluoromethyl)benzenemethylanolate-κO]aluminate, sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, trialkyl and triarylphosphonium tetrakis(pentafluorophenyl)borate, and trityl tetrakis(pentafluorophenyl)borate.

[0062] The co-catalyst can be in an amount of 1 / 20,000 mole to 1 / 500 mole per mole of the norbornene compound, preferably 1 / 10,000 mole to 1 / 1,000 mole, and more preferably 1 / 5,000 mole to 1 / 2,000 mole. This can further improve the yield of polynorbornene.

[0063] [Resettling process, etc.]

[0064] By the above steps, a reaction solution containing polynorbornene according to this embodiment can be obtained, and it can be further diluted with an organic solvent or the like as needed and used as a polymer solution. As the organic solvent, those exemplified in the reaction steps can be used, and it may be the same organic solvent as in the reaction steps, or a different organic solvent may be used.

[0065] Furthermore, this polymer solution can be added to a poor solvent to reprecipitate polynorbornene, remove unreacted monomers, and then dry and solidify to obtain polynorbornene powder. Examples of poor solvents include alcohols such as hexane, methanol, and isopropyl alcohol, as well as water, and can be used in combination.

[0066] The obtained polynorbornene powder can also be dissolved again in an organic solvent and used as a purified product (polynorbornene-containing solution). In particular, in applications where impurities and foreign substances are a concern, it is preferable to dissolve it again in an organic solvent. The concentration of polynorbornene in a polynorbornene-containing solution (100% by weight) is not particularly limited, but is approximately 30-70% by weight.

[0067] Use 15 to 150 times the weight of the polynorbornene-containing solution (100% by weight) of the above-mentioned solution as a poor solvent. The amount of poor solvent used varies depending on the type of solvent used for polymerization; 50 to 150 times the weight is used when using hydrocarbon-based solvents, and 15 to 50 times the weight is used when using ether-based solvents. By using this method, powdered polynorbornene can be obtained.

[0068] Since the method for producing polynorbornene in this embodiment does not use toluene and trifluorotoluene as solvents, the polynorbornene powder and polynorbornene-containing solution do not contain these solvents. Even when toluene or trifluorotoluene is used in the synthesis of norbornene, the raw material, these solvents are not used in the production method of polynorbornene. Therefore, the reaction solvent does not contain toluene or trifluorotoluene, or is below the detection limit in GC / MS measurement. Furthermore, since polynorbornene undergoes a purification process (such as a reprecipitation process), the polynorbornene powder and polynorbornene-containing solution do not contain toluene or trifluorotoluene, or are below the detection limit in GC / MS measurement. In particular, since the polynorbornene-containing solution can be prepared by dissolving the polymer powder obtained through the reprecipitation process in a solvent, a polynorbornene-containing solution free of toluene and trifluorotoluene can be obtained. In this embodiment, toluene and trifluorotoluene being below the detection limit means that the purified polynorbornene is below the detection limit when measured by gas chromatography-mass spectrometry (GC / MS).

[0069] The polynorbornene of this embodiment includes structural units represented by the following general formula (1a).

[0070] [ka]

[0071] In general formula (1a), R 1 , R 2 Q 1 , G 1 , G 2 , G 3 And m is equivalent to general formula (1).

[0072] According to the manufacturing method of this embodiment, polynorbornene with a low weight-average molecular weight can be obtained, and its weight-average molecular weight can preferably be 15,000 or less, more preferably 12,000 or less, and even more preferably 10,000 or less. The lower limit of the weight-average molecular weight is not particularly limited, but it can preferably be 2,000 or more, more preferably 3,000 or more, and even more preferably 5,000 or more. Because the weight-average molecular weight is within the above range, polynorbornene exhibits excellent compatibility with other materials, such as polyimide, making it suitable for obtaining photosensitive resin compositions.

[0073] The dispersion degree (Mw / Mn) of polynorbornene is, for example, 1.0 to 8.0, preferably 1.2 to 5.0, and more preferably 1.5 to 3.0. Having the dispersion degree within this range further enhances the compatibility of polynorbornene with other materials.

[0074] In this embodiment, the weight-average molecular weight of polynorbornene can be measured by obtaining a molecular weight distribution curve using GPC (Gel Permeation Chromatography). The weight-average molecular weight (Mw), number-average molecular weight (Mn), and degree of dispersion (PDI: Mw / Mn) of polynorbornene are calculated using polystyrene-converted values ​​obtained from a calibration curve of standard polystyrene (PS) obtained by GPC measurement. The measurement conditions for GPC are as follows, for example: Tosoh Corporation's gel permeation chromatography apparatus HLC-8320GPC Columns: TSK-GEL GMH, G2000H, SuperHM-M manufactured by Tosoh Corporation. Detector: RI detector for liquid chromatogram Measured temperature: 40 °C Solvent: THF Sample concentration: 5.0 mg / ml

[0075] Since the amount of palladium catalyst used in the reaction is small in the production method of this embodiment, the amount of residual palladium contained in the obtained polynorbornene powder can be reduced, and thus the dielectric properties such as the dielectric tangent are excellent.

[0076] <Photosensitive resin composition> The photosensitive resin composition of this embodiment contains the above-mentioned polynorbornene powder and polyimide.

[0077] [Polyimide] In the polyimide of this embodiment, at least one of both ends is preferably a group t represented by the following general formula (t), and more preferably both ends are the group t.

[0078] [Chemical formula]

[0079] In the general formula (t), R 5 and R 6 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. From the viewpoint of the effects of the present invention, an alkyl group having 1 or 2 carbon atoms is preferable, and an alkyl group having 1 carbon atom is more preferable. * represents a bond.

[0080] Q 2 represents a divalent organic group. As the divalent organic group, a known organic group can be used within the range where the effects of the present invention are achieved. For example, a divalent organic group represented by the following general formula (t-1) is preferable.

[0081] [Chemical formula]

[0082] In the general formula (t-1), R1 ~R 4 Each independently represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, R 1 and R 2 These are different groups, R 3 and R 4 These are different groups. R 1 ~R 4 From the viewpoint of the effects of the present invention, it is preferably an alkyl group having 1 to 3 carbon atoms.

[0083] X 1 X represents a single bond, -SO2-, -C(=O)-, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms, and there are multiple X groups. 1 They may be the same or different.

[0084] X 1 From the viewpoint of the effects of the present invention, it is preferably a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms, and more preferably a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms. * indicates a bond.

[0085] The polyimide of this embodiment includes a polyimide having a group t represented by the general formula (t) at at least one of its ends, and therefore exhibits excellent mechanical strength. Furthermore, since it does not undergo radical reactions and is photodimerizable, it exhibits even greater mechanical strength. Furthermore, the polyimide may include polyimides whose terminal ends are groups u represented by the following general formula (u).

[0086] [ka]

[0087] In general formula (u), X 1 , R 1 ~R 4This is equivalent to the general formula (t-1).

[0088] When the polyimide includes a polyimide comprising the group u, the ratio of the number of moles of group t to the total number of moles of group t and group u (t / t+u) can be 0.5 or higher, preferably 0.55 or higher, and more preferably 0.6 or higher. Within this range, the polyimide components that leach during development can be reduced.

[0089] The polyimide of this embodiment preferably includes a structural unit (a1) represented by the following general formula (a1) and a structural unit (a2) represented by the following general formula (a2).

[0090] [ka]

[0091] In general formula (a1), Y is a divalent organic group. As the divalent organic group, any known organic group can be used within the range that achieves the effects of the present invention. However, from the viewpoint of the effects of the present invention, it is preferable to use a divalent organic group selected from the following general formulas (a1-1), (a1-2), and (a1-3).

[0092] [ka]

[0093] In general formula (a1-1), R 7 and R 8 Each of these independently represents a hydrogen atom, a C1-C3 alkyl group, and a C1-C3 alkoxy group, and there are multiple R groups. 7 Multiple Rs exist. 8 They may be the same or different. R 7 and R 8 From the viewpoint of the effects of the present invention, it is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. R 9R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and there are multiple R groups. 9 They may be the same or different. R 9 From the viewpoint of the effects of the present invention, it is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. * indicates a bond.

[0094] In general formula (a1-2), R 10 and R 11 Each of these independently represents a hydrogen atom, a C1-C3 alkyl group, and a C1-C3 alkoxy group, and there are multiple R groups. 10 Multiple Rs exist. 11 They may be the same or different.

[0095] R 10 and R 11 From the viewpoint of the effects of the present invention, it is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably R 10 at least one of and R 11 At least one of them is an alkyl group having 1 to 3 carbon atoms, and more preferably three R 10 is an alkyl group having 1 to 3 carbon atoms and one R 10 It is a hydrogen atom and has three R 11 is an alkyl group having 1 to 3 carbon atoms and one R 11 is a hydrogen atom, and particularly preferably three R 10 It is a methyl group and one R 10 It is a hydrogen atom and has three R 11 It is a methyl group and one R 11 That is a hydrogen atom. * indicates a bond.

[0096] In general formulas (a1-3), Z represents an alkylene group having 1 to 5 carbon atoms, or a divalent aromatic group. * indicates a bond.

[0097] [ka]

[0098] In the general formula (a2), R 1 ~R 4 , X 1 is synonymous with the general formula (t-1).

[0099] Since the polyimide of the present embodiment contains a structural unit represented by the general formula (a2), the influence on the electrons of the imide ring is suppressed, hydrolysis of the polyimide is suppressed, mechanical strength such as elongation is excellent, and solubility in an organic solvent is also excellent. In other words, the polyimide of the present embodiment and the photosensitive resin composition containing the polyimide are excellent in the balance of these properties.

[0100] The polyimide may further contain a structural unit (a3) represented by the following general formula (a3).

[0101]

Chemical formula

[0102] In the general formula (a3), R 5 and R 6 each independently represent a hydrogen atom, a haloalkyl group having 1 to 4 carbon atoms, or a hydroxyl group, preferably a hydrogen atom or a haloalkyl group having 1 to 4 carbon atoms. When there are a plurality of R 5 they may be the same or different from each other, and when there are a plurality of R 6 they may be the same or different from each other.

[0103] X represents a single bond, an alkylene group having 1 to 4 carbon atoms, or a haloalkylene group having 1 to 4 carbon atoms, preferably a single bond or a haloalkylene group having 1 to 4 carbon atoms. m and n each independently represent 0 or 1.

[0104] In the general formula (t), as the divalent organic group of Q 2 it may be the structural unit (a3) represented by the general formula (a3). Specifically, a divalent organic group represented by the following general formula (t-2) can be cited.

[0105]

Chem.

[0106] In the general formula (t-2), R 5 , R 6 , X, m, and n are synonymous with the general formula (a3). * indicates a bond.

[0107] Specifically, the polyimide of the present embodiment can contain a structural unit 1 represented by the following general formula (1).

[0108]

Chem.

[0109] In the general formula (1), R 1 ~R 4 , X 1 is synonymous with the general formula (t-1), and Y is synonymous with the general formula (a1).

[0110] Specifically, the polyimide of the present embodiment may further contain a structural unit 2 represented by the following general formula (2) together with the structural unit 1.

[0111]

Chem.

[0112] In the general formula (2), R 5 ~R 6 , X, m, and n are synonymous with the general formula (a3), and Y is synonymous with the general formula (a1).

[0113] The weight average molecular weight of the polyimide of the present embodiment is 5,000 to 200,000, preferably 10,000 to 100,000.

[0114] [Photosensitizer] The photosensitive resin composition of the present embodiment can further contain a photosensitizer.

[0115] Examples of photosensitizers include benzophenone-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, benzyl-based photopolymerization initiators, and Michler-ketone-based photopolymerization initiators. Among these, benzophenone-based photopolymerization initiators or thioxanthone-based photopolymerization initiators are preferred.

[0116] Examples of benzophenone-based photopolymerization initiators include benzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, 4-phenylbenzophenone, isophthalphenone, and 4-benzoyl-4'-methyl-diphenyl sulfide. These benzophenones and their derivatives can improve the curing rate by using tertiary amines as hydrogen donors.

[0117] Examples of commercially available benzophenone-based photopolymerization initiators include SPEEDCUREMBP (4-methylbenzophenone), SPEEDCUREMBB (methyl-2-benzoylbenzoate), SPPEDCUREBMS (4-benzoyl-4'methyldiphenyl sulfide), SPPEDCUREPBZ (4-phenylbenzophenone), and SPPEDCUREEMK (4,4'-bis(diethylamino)benzophenone) (all trade names, manufactured by DKSH Japan Co., Ltd.).

[0118] Examples of thioxanthone-based photopolymerization initiators include thioxanthone, diethylthioxanthone, isopropylthioxanthone, and chlorothioxanthone. 2,4-diethylthioxanthone is preferred as diethylthioxanthone, 2-isopropylthioxanthone as isopropylthioxanthone, and 2-chlorothioxanthone as chlorothioxanthone. Among these, thioxanthone-based photopolymerization initiators containing diethylthioxanthone are even more preferred.

[0119] Examples of commercially available thioxanthone-based photopolymerization initiators include SpeedcureDETX (2,4-diethylthioxanthone), SpeedcureITX (2-isopropylthioxanthone), SpeedcureCTX (2-chlorothioxanthone), SPEEDCURECPTX (1-chloro-4-propylthioxanthone) (all trade names, manufactured by DKSH Japan Co., Ltd.), and KAYACUREDETX (2,4-diethylthioxanthone) (trade name, manufactured by Nippon Kayaku Co., Ltd.).

[0120] The amount of photosensitizer added is not particularly limited, but is preferably about 0.05 to 10% by mass of the total solid content of the photosensitive resin composition, more preferably about 0.1 to 7.5% by mass, and even more preferably about 0.2 to 5% by mass. By setting the amount of photosensitizer added within the above range, the patternability of the photosensitive resin layer containing the photosensitive resin composition can be improved, and the long-term storage properties of the photosensitive resin composition can be improved.

[0121] [Adhesion enhancer] The photosensitive resin composition of this embodiment may further contain an adhesion enhancer. This improves the adhesion between the resin film or pattern formed from the photosensitive resin composition and the substrate.

[0122] The adhesion aids that can be used are not particularly limited. For example, silane coupling agents such as aminosilane, epoxysilane, acrylicsilane, mercaptosilane, vinylsilane, ureidosilane, acid anhydride-functionalized silane, and sulfidesilane can be used. One silane coupling agent may be used alone, or two or more may be used in combination. Among these, epoxysilane (i.e., a compound containing both an epoxy moiety and a group that generates a silanol group by hydrolysis in one molecule) or acid anhydride-functionalized silane (i.e., a compound containing both an acid anhydride group and a group that generates a silanol group by hydrolysis in one molecule) is preferred. The group on the opposite side of the silane coupling agent can bond to polymer A or polyimide or become more compatible with the polymer, thereby further improving the adhesion of the resin film or pattern formed from the photosensitive resin composition to the substrate.

[0123] Examples of aminosilanes include bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, or N-phenyl-γ-aminopropyltrimethoxysilane.

[0124] Examples of epoxysilanes include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidylpropyltrimethoxysilane, etc.

[0125] Examples of acrylicsilanes include γ-(methacryloxypropyl)trimethoxysilane, γ-(methacryloxypropyl)methyldimethoxysilane, or γ-(methacryloxypropyl)methyldiethoxysilane. Examples of mercaptosilanes include 3-mercaptopropyltrimethoxysilane.

[0126] Examples of vinylsilanes include vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, or vinyltrimethoxysilane. Examples of ureidosilanes include 3-ureidopropyltriethoxysilane. Examples of acid anhydride-functionalized silanes include 3-trimethoxysilylpropyl succinic anhydride.

[0127] Examples of sulfidosilanes include bis(3-(triethoxysilyl)propyl) disulfide or bis(3-(triethoxysilyl)propyl) tetrasulfide. When using adhesion enhancers, you may use only one type, or two or more types in combination.

[0128] The amount of adhesion enhancer is typically 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, when the total solid content of the photosensitive resin composition is considered to be 100 parts by mass. It is believed that this range allows for sufficient adhesion, which is the effect of the adhesion enhancer, while maintaining a balance with other performance characteristics.

[0129] (solvent) The photosensitive resin composition according to this embodiment may contain a urea compound or an acyclic amide compound as a solvent. Preferably, the solvent contains a urea compound. This improves the adhesion between the cured product of the photosensitive resin composition and metals such as Al and Cu.

[0130] In this specification, a urea compound refers to a compound containing a urea bond, i.e., a urea bond. An amide compound refers to a compound containing an amide bond, i.e., an amide. Specifically, amides include primary amides, secondary amides, and tertiary amides.

[0131] Furthermore, in this embodiment, an acyclic structure means that the compound does not contain cyclic structures such as carbocyclic rings, inorganic rings, or heterocyclic rings. Examples of compounds that do not contain cyclic structures include linear structures and branched structures.

[0132] For urea compounds and acyclic amide compounds, those with a large number of nitrogen atoms in their molecular structure are preferred. Specifically, it is preferable that the molecular structure contains two or more nitrogen atoms. This increases the number of lone pairs of electrons. Therefore, adhesion to metals such as Al and Cu can be improved.

[0133] Specific structural examples of urea compounds include cyclic and acyclic structures. Of the above examples, an acyclic structure is preferred for the urea compound. This improves the adhesion between the cured photosensitive resin composition and metals such as Al and Cu. The reason for this is presumed to be as follows: Acyclic urea compounds are thought to form coordination bonds more easily than cyclic urea compounds. This is because acyclic urea compounds have fewer restrictions on molecular motion and a greater degree of freedom in molecular structure deformation compared to cyclic urea compounds. Therefore, when an acyclic urea compound is used, strong coordination bonds can be formed, improving adhesion.

[0134] Examples of urea compounds include tetramethylurea (TMU), 1,3-dimethyl-2-imidazolidinone, N,N-dimethylacetamide, tetrabutylurea, N,N'-dimethylpropyleneurea, 1,3-dimethoxy-1,3-dimethylurea, N,N'-diisopropyl-O-methylisourea, O,N,N'-triisopropylisourea, O-tert-butyl-N,N'-diisopropylisourea, O-ethyl-N,N'-diisopropylisourea, and O-benzyl-N,N'-diisopropylisourea. One or more of the above specific examples of urea compounds can be used in combination. As the urea compound, it is preferable to use one or more selected from the group consisting of tetramethylurea (TMU), tetrabutylurea, 1,3-dimethoxy-1,3-dimethylurea, N,N'-diisopropyl-O-methylisourea, O,N,N'-triisopropylisourea, O-tert-butyl-N,N'-diisopropylisourea, O-ethyl-N,N'-diisopropylisourea, and O-benzyl-N,N'-diisopropylisourea, with tetramethylurea (TMU) being more preferable. This allows for the formation of strong coordination bonds and improves adhesion.

[0135] Examples of acyclic amide compounds include 3-methoxy-N,N-dimethylpropanamide, N,N-dimethylformamide, N,N-dimethylpropionamide, N,N-diethylacetamide, 3-butoxy-N,N-dimethylpropanamide, and N,N-dibutylformamide. The photosensitive resin composition according to this embodiment may contain, as a solvent, a urea compound, an acyclic amide compound, or a solvent that does not contain a nitrogen atom.

[0136] Examples of solvents that do not contain nitrogen atoms include ether-based solvents, acetate-based solvents, alcohol-based solvents, ketone-based solvents, lactone-based solvents, carbonate-based solvents, sulfone-based solvents, ester-based solvents, and aromatic hydrocarbon-based solvents. One or more of the above specific examples can be used as solvents that do not contain nitrogen atoms.

[0137] Examples of the above-mentioned ether-based solvents include propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, and 1,3-butylene glycol-3-monomethyl ether.

[0138] Examples of the acetate-based solvents mentioned above include propylene glycol monomethyl ether acetate (PGMEA), methyl lactate, ethyl lactate, butyl lactate, and methyl-1,3-butylene glycol acetate.

[0139] Examples of the above-mentioned alcohol-based solvents include tetrahydrofurfuryl alcohol, benzyl alcohol, 2-ethylhexanol, butanediol, and isopropyl alcohol. Examples of the ketone solvents mentioned above include cyclopentanone, cyclohexanone, diacetone alcohol, and 2-heptanone. Examples of the lactone-based solvents mentioned above include γ-butyrolactone (GBL) and γ-valerolactone. Examples of the carbonate-based solvents mentioned above include ethylene carbonate and propylene carbonate. Examples of the above-mentioned sulfone-based solvents include dimethyl sulfoxide (DMSO) and sulfolane. Examples of the ester solvents mentioned above include methyl pyruvate, ethyl pyruvate, and methyl-3-methoxypropionate. Examples of the above-mentioned aromatic hydrocarbon solvents include mesitylene, toluene, and xylene.

[0140] Of the solvents mentioned above, the more preferred solvents are PGMEA and cyclopentanone. Using these solvents can improve the solubility of polymer A (polynorbornene) and polyimide (polyimide).

[0141] (Surfactants) The photosensitive resin composition according to this embodiment may further contain a surfactant.

[0142] The surfactants are not limited to, but specifically include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; F-Top EF301, F-Top EF303, F-Top EF352 (manufactured by Shin Akita Chemical Co., Ltd.), Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F444, Megafac F470, Examples include fluorinated surfactants commercially available under names such as Megafac F471, Megafac F475, Megafac F482, Megafac F477 (manufactured by DIC Corporation), Florard FC-430, Florard FC-431, Novec FC4430, Novec FC4432 (manufactured by 3M Japan), Surflon S-381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (manufactured by AGC Seimi Chemical Co., Ltd.); organosiloxane copolymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); and (meth)acrylic acid copolymer Polyflow No. 57 and 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

[0143] Among these, it is preferable to use a fluorinated surfactant having a perfluoroalkyl group. As a fluorinated surfactant having a perfluoroalkyl group, it is preferable to use one or more selected from the above specific examples: Megafac F171, Megafac F173, Megafac F444, Megafac F470, Megafac F471, Megafac F475, Megafac F482, Megafac F477 (manufactured by DIC Corporation), Surflon S-381, Surflon S-383, Surflon S-393 (manufactured by AGC Seimi Chemical Co., Ltd.), Novec FC4430, and Novec FC4432 (manufactured by 3M Japan).

[0144] Furthermore, silicone-based surfactants (such as polyether-modified dimethylsiloxane) can also be preferably used as surfactants. Specific examples of silicone-based surfactants include the SH series, SD series, and ST series from Toray Dow Corning, the BYK series from BIC Chemie Japan, the KP series from Shin-Etsu Chemical Co., Ltd., the Disform® series from NOF Corporation, and the TSF series from Toshiba Silicone Co., Ltd.

[0145] The upper limit of the surfactant content in the photosensitive resin composition is preferably 1% by mass (10,000 ppm) or less, more preferably 0.5% by mass (5,000 ppm) or less, and even more preferably 0.1% by mass (1,000 ppm) or less, relative to the total amount of the photosensitive resin composition (including the solvent).

[0146] Furthermore, there is no particular lower limit for the surfactant content in the photosensitive resin composition, but from the viewpoint of obtaining sufficient effects from the surfactant, for example, it should be 0.001% by mass (10 ppm) or more relative to the total amount of the photosensitive resin composition (including the solvent). By appropriately adjusting the amount of surfactant, it is possible to improve application properties and the uniformity of the coating film while maintaining other performance characteristics.

[0147] (Antioxidant) The photosensitive resin composition according to this embodiment may further contain an antioxidant. One or more antioxidants selected from phenol-based antioxidants, phosphorus-based antioxidants, and thioether-based antioxidants can be used. The antioxidant can suppress the oxidation of the resin film formed by the photosensitive resin composition.

[0148] Examples of phenol-based antioxidants include pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,9-bis{2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}2,4,8,10-tetraoxaspiro[5,5]undecane, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, and 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate [(3,5-di-t-butyl-4-hydroxybenzyl)benzene], 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl(3,5-di-t-butyl-4-hydroxyphenyl)propionate, distearyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate, thiodiethylene glycol bis[(3,5-di-t-butyl-4-hydroxyphenyl)propionate 4,4'-thiobis(6-t-butyl-m-cresol), 2-octylthio-4,6-di(3,5-di-t-butyl-4-hydroxyphenoxy)-s-triazine, 2,2'-methylenebis(4-methyl-6-t-butyl-6-butylphenol), 2,-2'-methylenebis(4-ethyl-6-t-butylphenol), bis[3,3-bis(4-hydroxy-3-t-butylphenyl)butyric acid] glycol ester, 4,4'-butylidenebis(6-t-butyl-m-cresol), 2,2'-ethylidenebis(4,6-di- t-butylphenol), 2,2'-ethylidenebis(4-s-butyl-6-t-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, bis[2-t-butyl-4-methyl-6-(2-hydroxy-3-t-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)isocyanurate, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-Tris[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 2-t-butyl-4-methyl-6-(2-acryloyloxy-3-t-butyl-5-methylbenzyl)phenol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4-8,10-tetraoxaspiro[5,5] Undecane-bis[β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate], triethyleneglycol-bis[β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate], 1,1'-bis(4-hydroxyphenyl)cyclohexane, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 2,2'-methylenebis(6-(1 -methylcyclohexyl)-4-methylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 3,9-bis(2-(3-t-butyl-4-hydroxy-5-methylphenylpropionyloxy)1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-bis(3,5-di-t-butyl-4-hydroxybenzyl) Examples include ruphaide, 4,4'-thiobis(6-t-butyl-2-methylphenol), 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2,4-dimethyl-6-(1-methylcyclohexyl, styrenelated phenol, 2,4-bis((octylthio)methyl)-5-methylphenol, etc.

[0149] Examples of phosphorus-based antioxidants include bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, tris(2,4-di-t-butylphenyl phosphite), tetrakis(2,4-di-t-butyl-5-methylphenyl)-4,4'-biphenylenediphosphonite, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, bis-(2,6-dicumylphenyl)pentaerythritol diphosphite, and 2,2-methylenebi. Examples include s(4,6-di-t-butylphenyl)octyl phosphite, tris(mixed mono- and di-nonylphenyl phosphite), bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methoxycarbonylethylphenyl)pentaerythritol diphosphite, and bis(2,6-di-t-butyl-4-octadecyloxycarbonylethylphenyl)pentaerythritol diphosphite.

[0150] Examples of thioethyl antioxidants include dilauryl-3,3'-thiodipropionate, bis(2-methyl-4-(3-n-dodecyl)thiopropionyloxy)-5-t-butylphenyl) sulfide, distearyl-3,3'-thiodipropionate, and pentaerythritol-tetrakis(3-lauryl)thiopropionate.

[0151] (Preparation of photosensitive resin composition) The method for preparing the photosensitive resin composition in this embodiment is not limited, and known methods can be used depending on the components contained in the photosensitive resin composition. For example, the above components can be prepared by mixing and dissolving them in a solvent.

[0152] (Photosensitive resin composition, cured film) The photosensitive resin composition according to this embodiment is used by coating the photosensitive resin composition onto a surface having a metal such as Al or Cu, then pre-baking and drying to form a resin film, then exposing and developing the resin film to a desired shape, and finally post-baking to cure the resin film and form a cured film.

[0153] When producing the above permanent film, pre-baking conditions can include, for example, heat treatment at a temperature of 50°C to 150°C for 30 seconds to 1 hour. Post-baking conditions can include, for example, heat treatment at a temperature of 150°C to 250°C for 30 minutes to 10 hours.

[0154] The viscosity of the photosensitive resin composition according to this embodiment can be appropriately set according to the desired thickness of the resin film. The viscosity of the photosensitive resin composition can be adjusted by adding a solvent. When adjusting the viscosity, it is necessary to keep the content of urea compounds and acyclic amide compounds in the solvent constant.

[0155] The upper limit of the viscosity of the photosensitive resin composition according to this embodiment may be, for example, 5000 mPa·s or less, 4000 mPa·s or less, or 3000 mPa·s or less. The lower limit of the viscosity of the photosensitive resin composition according to this embodiment may be, for example, 10 mPa·s or more, or 50 mPa·s or more, depending on the desired thickness of the resin film.

[0156] The film obtained from the photosensitive resin composition of this embodiment has an elongation rate measured by tensile testing using a Tensilon tester, with a maximum value of 10-200%, preferably 20-150%, and an average value of 1-150%, preferably 2-120%. The film obtained from the photosensitive resin composition of this embodiment can have a tensile strength of 30 to 300 MPa, preferably 50 to 200 MPa.

[0157] Thus, the photosensitive resin composition of this embodiment can provide cured products such as films with excellent mechanical strength. The reason for this is not clear, but it is presumed to be due to the excellent properties of the rigid polyimide of the present invention.

[0158] The film made from the photosensitive resin composition of this embodiment exhibits excellent low dielectric loss tangent, with a dielectric loss tangent (tanδ) of 0.008 or less when measured at a frequency of 10 GHz, preferably 0.007 or less, and more preferably 0.006 or less.

[0159] The film made from the photosensitive resin composition of this embodiment has suppressed curing shrinkage, and its linear thermal expansion coefficient (CTE) can be 200 ppm / °C or less, preferably 150 ppm / °C or less.

[0160] (Application) The photosensitive resin composition (negative-type photosensitive resin composition) of this embodiment is used to form resin films for semiconductor devices such as permanent films and resists. Among these, it is preferable to use it in applications where a permanent film is used, from the viewpoint of achieving a good balance between improving the adhesion between the photosensitive resin composition and the Al pad after pre-baking and suppressing the generation of residue of the photosensitive resin composition during development, from the viewpoint of improving the adhesion between the cured film of the photosensitive resin composition after post-baking and the metal, and in addition, from the viewpoint of improving the chemical resistance of the photosensitive resin composition after post-baking.

[0161] In this embodiment, the resin film includes a cured film of a photosensitive resin composition. That is, the resin film according to this embodiment is obtained by curing a photosensitive resin composition.

[0162] The above-mentioned permanent film is composed of a resin film obtained by pre-baking, exposing, and developing a photosensitive resin composition, patterning it into a desired shape, and then curing it by post-baking. The permanent film can be used as a protective film, interlayer film, or dam material for semiconductor devices.

[0163] The above-mentioned resist is composed of a resin film obtained by, for example, applying a photosensitive resin composition to an object to be masked by the resist using methods such as spin coating, roll coating, flow coating, dip coating, spray coating, or doctor coating, and then removing the solvent from the photosensitive resin composition. An example of a semiconductor device according to this embodiment is shown in Figure 1.

[0164] The semiconductor device 100 according to this embodiment may be a semiconductor device comprising the resin film described above. Specifically, one or more of the group consisting of the passivation film 32, insulating layer 42, and insulating layer 44 in the semiconductor device 100 may be a resin film containing the cured product of this embodiment. Here, it is preferable that the resin film is the permanent film described above.

[0165] The semiconductor device 100 is, for example, a semiconductor chip. In this case, for example, a semiconductor package is obtained by mounting the semiconductor device 100 on a wiring board via bumps 52.

[0166] The semiconductor device 100 comprises a semiconductor substrate on which semiconductor elements such as transistors are provided, and a multilayer wiring layer (not shown) provided on the semiconductor substrate. The uppermost layer of the multilayer wiring layer is provided with an interlayer insulating film 30 and an uppermost wiring 34 provided on the interlayer insulating film 30. The uppermost wiring 34 is made of, for example, aluminum Al. A passivation film 32 is also provided on the interlayer insulating film 30 and the uppermost wiring 34. An opening is provided in a part of the passivation film 32 that exposes the uppermost wiring 34.

[0167] A rewiring layer 40 is provided on the passivation film 32. The rewiring layer 40 includes an insulating layer 42 provided on the passivation film 32, rewiring 46 provided on the insulating layer 42, and an insulating layer 44 provided on the insulating layer 42 and the rewiring 46. The insulating layer 42 has openings formed therein that connect to the uppermost wiring 34. The rewiring 46 is formed on the insulating layer 42 and within the openings provided in the insulating layer 42 and is connected to the uppermost wiring 34. The insulating layer 44 has openings that connect to the rewiring 46.

[0168] Bumps 52 are formed within the openings provided in the insulating layer 44, for example, via a UBM (Under Bump Metallurgy) layer 50. The semiconductor device 100 is connected to a wiring board or the like via the bumps 52. Although embodiments of the present invention have been described above, these are merely examples, and various other configurations can be adopted as long as they do not impair the effects of the present invention. [Examples]

[0169] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

[0170] [Synthesis Example 1] (Synthesis of 1-[4-(5-2-norbornyl)butyl]-3,4-dimethylpyrrole-2,5-dione (NBBuDMMI)) In a 500 mL round-bottom flask, dimethyl maleic anhydride (42.6 g, 0.34 mol) was dissolved in toluene (300 mL) at room temperature. To remove oxygen, the solution was placed under a nitrogen atmosphere. The reaction flask was placed in an ice bath to prevent excessive heating due to the exothermic reaction. Once the dimethyl maleic anhydride was dissolved, a dropping funnel containing 5-norbornene-2-butylamine (49.6 g, 0.30 mol) was attached, and the norbornene compound was added dropwise to the reaction flask over 3 hours. The dropping funnel was removed, and a Dean-Stark tube and reflux condenser were attached to the flask. The solution was heated and refluxed in an oil bath set to 125°C, and the reactants were stirred at that temperature for 18 hours. During this time, approximately 6 mL of water was collected in the Dean-Stark tube. The flask was removed from the oil bath and cooled to room temperature. The toluene solvent was removed using an evaporator to obtain a yellow oily substance. The crude product was placed on a flash chromatography column (250 g of silica gel) and eluted using a solvent mixture of 1.7 liters of cyclohexane / ethyl acetate (95 / 5 wt ratio). The eluent was removed using an evaporator, and then dried under vacuum at 45°C for 18 hours to obtain 80.4 g (yield 92.7%) of the target product. The reaction equation is shown below.

[0171] [ka]

[0172] [Hansen solubility parameters of solvents] The Hansen solubility parameters for solvents and mixed solvents were obtained by inputting molecular structures into the HSPiP computer software database or the HSPiP DIY program. For mixed solvents, the solubility parameters were calculated using the following formula. In the following formula, the volume ratio of solvent 1 is a, and the Hansen solubility parameters are expressed using the dispersion term (δD1), polarization term (δP1), and hydrogen bonding term (δH1). The volume ratio of solvent 2 is b, and the Hansen solubility parameters are expressed using the dispersion term (δD2), polarization term (δP2), and hydrogen bonding term (δH2). Table 1 shows the dispersion term (δD), polarization term (δP), and hydrogen bonding term (δH) for the polymer (pNBBuDMMI), solvent, and mixed solvent, and Table 2 shows the Hansen distance Ra between the polymer (pNBBuDMMI) and the mixed solvent.

[0173]

number

[0174] [Hansen solubility parameters for polynorbornene (pNBBuDMMI)] The Hansen solubility parameter a of polynorbornene was measured using the following method. The polynorbornene used in the following measurements was the homopolymer of NBBuDMMI obtained in Synthesis Example 1. Note that the dispersion term (δD), polarization term (δP), and hydrogen bonding term (δH) of polynorbornene are not affected by the weight-average molecular weight of the polynorbornene. [method] In a 5 ml glass container, add 1 ml of any solvent selected from the evaluation solvents listed below to 0.05 g of polynorbornene, and after stirring with a mixing rotor for 1 hour, visually evaluate the dispersibility in the following three stages. Input all evaluation solvents and the evaluation results for dispersibility in each solvent into the Sphere program of the computer software HSPiP (version 5.2.02) and calculate the Hansen solubility parameter. (Solvent for evaluation) Hexane, cyclohexane, toluene, benzyl benzoate, propylene carbonate, 1-hexene, methyl ethyl ketone, acetone, acetonitrile, ethyl acetate, propylene glycol monomethyl ether acetate, cyclohexanol, isopropyl alcohol, methanol (evaluation) 1: Dissolve completely. 2: It partially dissolves. 6: Does not dissolve.

[0175] The measurement results showed that the dispersion term (δD) of the Hansen solubility parameter for polynorbornene was 18.9 MPa. 1 / 2 The polarization term (δP) is 5.5 MPa.1 / 2 The hydrogen bonding term (δH) is 7.2 MPa. 1 / 2 That was the case. Table 1 shows the dispersion term (δD), polarization term (δP), and hydrogen bonding term (δH) for polynorbornene (pNBBuDMMI) and the solvent, and Table 2 shows the difference between the Hansen solubility parameter a of polynorbornene (pNBBuDMMI) and the Hansen solubility parameter b of the solvent.

[0176] [Table 1]

[0177] [Table 2]

[0178] [Example 1] Synthesis of polynorbornene 1 After venting a reaction vessel of appropriate size, equipped with a stirrer and condenser, with nitrogen for 1 hour, 1-[4-(5-2-norbornyl)butyl]-3,4-dimethylpyrrole-2,5-dione (NBBuDMMI) (24.60 g, 90 mmol) and triethylsilane (3.14 g, 27 mmol) were added. Further, cyclopentyl methyl ether (CPME) (16.04 g) and ethyl acetate (EA) (1.98 g) were added to obtain the reaction solution. The reaction solution was heated to 70°C with stirring under a nitrogen flow (50 mL / min). A solution was prepared by dissolving the catalyst (palladium(II)(acetonitrile)bis(triisopropylphosphine)acetatetetrakis(2,3,4,5,6-pentafluorophenyl) borate, Pd-1206) (0.0434 g) and the co-catalyst (N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, DANFABA) (0.0288 g) in ethyl acetate (EA) (3.37 g). These solutions were then added to the reaction solution in a molar ratio of NBBuDMMI:catalyst:co-catalyst = 2500:1:1. Polymerization was carried out at 70°C for 3 hours, and after polymerization, the reaction was stopped by allowing it to cool. The obtained polymerization solution was diluted with tetrahydrofuran to prepare a diluent, and then the diluent was added dropwise to a methanol solution to precipitate a white solid. The obtained white solid was collected and vacuum-dried at 50°C to obtain 20.02 g of polymer (polynorbornene 1). The toluene content of polynorbornene-1, as measured by the method described later, was below the detection limit.

[0179] [Example 2] Synthesis of polynorbornene 2 In Example 1, CPME was replaced with 4-methyltetrahydropyran (MTHP), and the synthesis was carried out in the same manner as in Example 1, according to the conditions in Table 3 below. The toluene content of polynorbornene-2, as measured by the method described later, was below the detection limit.

[0180] [Example 3] Synthesis of polynorbornene 3 In Example 1, CPME was replaced with cyclohexane (CH), and the synthesis was carried out in the same manner as in Example 1, according to the conditions in Table 3 below. The toluene content of polynorbornene-3, as measured by the method described later, was below the detection limit.

[0181] [Example 4] Synthesis of polynorbornene 4 In Example 1, CPME was replaced with methylcyclohexane (MCH), and the synthesis was carried out in the same manner as in Example 1, according to the conditions in Table 3 below. The toluene content of polynorbornene-4, as measured by the method described later, was below the detection limit.

[0182] [Example 5] Synthesis of polynorbornene 5 The synthesis was carried out in the same manner as in Example 1, according to the conditions in Table 3 below. The toluene content of polynorbornene-5, as measured by the method described later, was below the detection limit.

[0183] [Comparative Example 1] Synthesis of polynorbornene 6 The cyclopentyl methyl ether of Example 1 was changed to toluene (Tol), and it was synthesized in the same manner as in Example 1 according to the conditions shown in Table 3 below. The toluene content of polynorbornene 6 measured by the method described below was 350 ppm. In addition, the polynorbornene obtained in any of the examples did not contain trifluorotoluene.

[0184] (Weight-average molecular weight (Mw) · Number-average molecular weight (Mn) · Molecular weight distribution (PDI)) In Synthesis Example 1, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (PDI: Mw / Mn) were determined using the polystyrene conversion values obtained from the calibration curve of standard polystyrene (PS) obtained by GPC measurement. The measurement conditions are as follows. Gel permeation chromatography apparatus HLC-8320GPC manufactured by Tosoh Corporation Column: TSK-GEL Supermultipore HZ-M manufactured by Tosoh Corporation Detector: RI detector for liquid chromatogram Measurement temperature: 40 °C Solvent: THF Sample concentration: 5.0 mg / ml

[0185] (Conversion rate) In Examples 1 to 5 and Comparative Example 1, the conversion rate of NBBuDMMI was derived by sampling the reaction solution before and after polymerization and performing gas chromatography (GC) measurement. The measurement conditions are as follows. Gas chromatography apparatus GC-2030 manufactured by SHIMADZU Corporation Column: SH-Rxi-1HT Detector: FID Measurement conditions: 210 °C (30 minutes) Internal standard: Methyl amyl ketone Dilution solvent: Mesitylene Sample concentration: 5.0 mg / ml

[0186] (Toluene content) In Examples 1-5 and Comparative Example 1, the toluene content was determined by measuring the content of purified polynorbornene using gas chromatography-mass spectrometry (GC / MS). The detection limit was approximately 10 ppm or less. Column: F-Lab UA5-30M (0.25mm x 30m, film thickness: 250mm) Carrier gas: He, 1 ml / min Column temperature: 40°C (5 mins) → 10°C / min → 300°C (9 mins) Detector: MS Inlet temperature: 210℃ Split ratio: 50:1 Sample weight: 2.0 mg Ion source: EI, m / z 25–800

[0187] [Table 3]

[0188] [Synthesis Example 1] (Synthesis of polyimides) The following compounds were used in the synthesis of the polyimides described below. 4,4-diamino-3,3-diethyl-5,5-dimethyldiphenylmethane (hereinafter also referred to as MED-J), represented by the following formula [ka]

[0189] The following formula represents 4-[4-(1,3-dioxoisobenzofuran-5-ylcarbonyloxy)-2,3,5-trimethylphenyl]-2,3,6-trimethylphenyl 1,3-dioxoisobenzofuran-5-carboxylate (hereinafter also referred to as TMPBP-TME) [ka]

[0190] First, 43.99 g (155.8 mmol) of MED-J and 89.22 g (144.2 mmol) of TMPBP-TME were placed in a reaction vessel of appropriate size equipped with a stirrer and condenser. Then, 399.64 g of γ-butyrolactone (hereinafter also referred to as GBL) was added to the reaction vessel. After aeration with nitrogen for 10 minutes, the temperature was raised to 60°C while stirring, and the reaction was carried out for 1 hour. Prior to this, a solution was prepared by dissolving 8.73 g (69.2 mmol) of dimethyl maleic anhydride in 26.19 g of gamma butyrolactone. This solution was added to the reaction vessel, and the reaction was carried out for another 30 minutes. The reaction was then carried out at 175°C for 3 hours to polymerize the diamine and acid anhydride, and a polymerization solution was prepared with sealed ends. The obtained polymerization solution was diluted with tetrahydrofuran to prepare a dilution, and then the dilution was added dropwise to a methanol solution to precipitate a white solid. The obtained white solid was collected and vacuum-dried at 80°C to obtain 125.88 g of polyimide. GPC analysis of the polyimide revealed a weight-average molecular weight (Mw) of 74,000, a polydispersity (weight-average molecular weight Mw / number-average molecular weight Mn) of 2.62, and a end-capacity of 65%. The resulting polyimide contained repeating units represented by the following formula, with dimethylmaleimide groups at its termini. [ka]

[0191] [Example 6] The following components were used in the preparation of the following photosensitive resin composition. • Photosensitive agent: 1-chloro-4-propoxythioxanthone (manufactured by Lambson, UK; brand name: SPEEDCURE CPTX) • Solvent: Cyclopentanone • Adhesion enhancer: 3-trimethoxysilylpropyl succinic anhydride (manufactured by Shin-Etsu Chemical Co., Ltd., product name "X-12-967C") A photosensitive resin composition was prepared by mixing the components listed in Table 4. The obtained photosensitive resin composition was spin-coated on the surface of a silicon wafer so that the film thickness after drying was 10 μm. After pre-baking at 120 °C for 4 minutes, it was exposed with a high-pressure mercury lamp at 1500 mJ / cm 2 and then cured at 200 °C for 120 minutes in a nitrogen atmosphere to prepare a film.

[0192] [Polymer compatibility (compatibility with polyimide of polynorbornene)] After pre-baking the obtained photosensitive resin composition at 120 °C for 4 minutes, it was visually confirmed under a fluorescent lamp whether the surface was cloudy, and evaluated according to the following criteria. 〇: Compatible. ×: Incompatible.

[0193] [Dielectric tangent Df] The photosensitive resin composition of Example 6 was applied on a substrate, and the coating film was dried at 120 °C for 10 minutes, exposed to PLA (540 mJ), and cured at 200 °C for 2 hours in a nitrogen atmosphere to obtain a film with a thickness of 100 μm. For the obtained film, the dielectric tangent at 10 GHz was measured by the cavity resonator method.

[0194] [Evaluation of patterning characteristics] It was confirmed as follows that the photosensitive resin composition of Example 6 could be sufficiently patterned by exposure and development. The photosensitive resin composition of Example 6 was applied on an 8-inch silicon wafer using a spin coater. After application, it was pre-baked at 120 °C for 4 minutes on a hot plate in the atmosphere to obtain a coating film with a thickness of about 8.0 μm. This coating film was irradiated with i-line through a mask on which a via pattern with a width of 20 μm was drawn. For the irradiation, an i-line stepper (manufactured by Nikon Corporation, NSR-4425i) was used. After exposure, cyclopentanone was used as the developer, and spray development was performed for 120 seconds to dissolve and remove the unexposed portion to obtain a via pattern. The cross-section of the obtained via pattern was observed using a desktop SEM. The width at the height between the bottom surface and the opening of the via pattern was defined as the via width and evaluated according to the following criteria. Excellent patternability: 20μm via pattern opens. Poor patterning: 20μm via pattern does not open. The coating film obtained from the photosensitive resin composition of Example 6 exhibited good patternability.

[0195] [Table 4] [Explanation of Symbols]

[0196] 30 Interlayer insulating film 32 Passivation membrane 34 Top layer wiring 40 Redistribution layer 42 Insulating layer 44 Insulating layer 46 Rewiring 50 UBM layers 52 Bump 100 Semiconductor Devices

Claims

1. The process includes polymerizing a norbornene-based compound in a solvent in the presence of a palladium catalyst and a chain transfer agent to obtain polynorbornene. The solvent does not contain toluene and trifluorotoluene, or its levels are below the detection limit in GC / MS measurements. A method for producing polynorbornene, wherein the difference between the Hansen solubility parameter a of the polynorbornene and the Hansen solubility parameter b of the solvent is 8 or less.

2. The method for producing polynorbornene according to claim 1, wherein the norbornene compound includes a compound represented by the following general formula (1). 【Chemistry 1】 (In general formula (1), R １ and R ２ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q １ This indicates a single bond or a divalent organic group, G １ G ２ , and G ３ Each of these independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, and m is 0, 1, or 2.

3. The method for producing polynorbornene according to claim 1 or 2, wherein the chain transfer agent comprises at least one selected from a compound represented by the following general formula (a), formic acid, and oxalic acid. 【Chemistry 2】 (In general formula (a), R １ , R ２ and R ３ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)

4. In general formula (1), R １ , R ２ and R ３ The method for producing polynorbornene according to claim 3, wherein each of the elements independently represents an alkyl group having 1 to 3 carbon atoms.

5. The method for producing polynorbornene according to any one of claims 1 to 4, wherein the solvent is a mixed solvent of two or more types.

6. The method for producing polynorbornene according to any one of claims 1 to 5, wherein the solvent comprises at least one selected from ether-based solvents and hydrocarbon-based solvents that do not contain aromatic rings.

7. The ether-based solvent comprises at least one selected from cyclopentyl methyl ether and methyltetrahydropyran. The method for producing polynorbornene according to claim 6, wherein the hydrocarbon solvent that does not contain an aromatic ring comprises at least one selected from cyclohexane and methylcyclohexane.

8. A method for producing polynorbornene according to any one of claims 1 to 7, wherein, when the solvent is a mixed solvent of two types, the difference between the Hansen solubility parameter a of the norbornene compound and the Hansen solubility parameter c of the mixed solvent of two types is 8 or less.

9. The method for producing polynorbornene according to any one of claims 1 to 8, wherein the solvent is a mixed solvent of at least one selected from cyclopentyl methyl ether, methyltetrahydropyran, cyclohexane, and methylcyclohexane, and ethyl acetate.

10. A method for producing polynorbornene according to any one of claims 1 to 9, wherein the palladium catalyst is used in an amount of 1 / 5000 mole to 1 / 2000 mole per mole of the norbornene compound.

11. Furthermore, the method for producing polynorbornene according to any one of claims 1 to 9, comprising the step of mixing the polynorbornene obtained in the polymerization step with a poor solvent for the polynorbornene to reprecipitate the powdered polynorbornene.

12. A method for producing polynorbornene according to claim 11, comprising a step of diluting the polynorbornene obtained in the polymerization step before the reprecipitation step.

13. A polynorbornene-containing solution comprising polynorbornene containing the structural unit represented by the following general formula (1a), and free from toluene and trifluorotoluene, or below the detection limit in GC / MS measurement. 【Transformation 3】 (In general formula (1a), R １ and R ２ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q １ This indicates a single bond or a divalent organic group, G １ G ２ , and G ３ Each of these independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, and m is 0, 1, or 2.

14. The polynorbornene-containing solution according to claim 13, wherein the weight-average molecular weight of the polynorbornene is 15,000 or less.

15. Polynorbornene powder containing structural units represented by the following general formula (1a), which are free of toluene and trifluorotoluene or are below the detection limit in GC / MS measurement. 【Chemistry 4】 (In general formula (1a), R １ and R ２ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q １ This indicates a single bond or a divalent organic group, G １ G ２ , and G ３ Each of these independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, and m is 0, 1, or 2.

16. The polynorbornene powder according to claim 15, wherein the weight-average molecular weight of the polynorbornene is 15,000 or less.

17. Polynorbornene powder according to claim 15 or 16, Polyimide and A photosensitive resin composition containing [the specified element].

18. The photosensitive resin composition according to claim 17, wherein at least one of the ends of the polyimide is a group represented by the following general formula (t). 【Transformation 5】 (In general formula (t), R ５ and R ６ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q ２ ( indicates a divalent organic group. * indicates a bond.)

19. Furthermore, the photosensitive resin composition according to claim 17 or 18, further comprising a photosensitizer.

20. A cured film comprising a cured product of the photosensitive resin composition according to any one of claims 17 to 19.

21. A semiconductor device comprising a resin film containing a cured product of the photosensitive resin composition according to any one of claims 17 to 19.

22. Interlayer insulating film and A resin film provided on the interlayer insulating film, comprising a cured product of the photosensitive resin composition according to any one of claims 17 to 19, The rewiring embedded in the aforementioned resin film, The semiconductor device according to claim 21, characterized by comprising:

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