TW202106734A - Photosensitive resin composition, resin film and electronic device - Google Patents

Abstract

A photosensitive resin composition, containing a copolymer represented by general formula (1), a crosslinking agent, and a photosensitizer.

Description

Photosensitive resin composition, resin film and electronic device

The present invention relates to a photosensitive resin composition, resin film and electronic device. More specifically, the present invention relates to a photosensitive resin composition, a resin film composed of a cured product of the photosensitive film-forming composition, and an electronic device provided with the resin film as a permanent film.

In recent years, photosensitive resin compositions that can be patterned by active energy rays such as ultraviolet rays and electron beams have been widely used in the fields of various coatings, printing, paints, adhesives, and electronic materials such as printed wiring boards. For example, Patent Document 1 discloses a photosensitive copolymer comprising a monomer having a cyclic hydrocarbon group, an unsaturated polybasic acid anhydride such as maleic anhydride, a copolymerizable monomer such as vinyl toluene, and a monomer having a hydroxyl group. A resin composition and a color filter formed by a cured film of the resin composition.

[Patent Document 1] Japanese Patent No. 5588503

(Problems to be solved by the invention)

However, as a result of research conducted by the present inventors, it is determined that the photosensitive resin composition described in Patent Document 1 has room for improvement in the transparency of the cured product. (The way to solve the problem)

The inventors found that by using a copolymer containing a specific structural unit as a base resin, a photosensitive resin composition whose cured product has high transparency and excellent heat discoloration resistance can be obtained, thereby completing the present invention.

According to the present invention, a photosensitive resin composition can be provided, which includes: A copolymer represented by the general formula (1); Crosslinking agent; and Photosensitizer.

通式(1)中， l及m分別表示共聚物中的A及B的莫耳含有率， l+m=1， X為氫或碳數1以上且30以下的有機基， Y為-SR_5a ，S為硫原子，R_5a 為碳數1以上且30以下的有機基， A包含由以下式(A1)表示之構造單元， B包含由式(B1)～(B6)表示之構造單元中的至少1個，[化1]

In the general formula (1), l and m respectively represent the molar content of A and B in the copolymer, l+m=1, X is hydrogen or an organic group with 1 to 30 carbon atoms, and Y is -SR _5a , S is a sulfur atom, R _5a is an organic group with a carbon number of 1 or more and 30 or less, A includes the structural unit represented by the following formula (A1), and B includes the structural unit represented by the formula (B1) to (B6) At least one of

通式(A1)中，R₁ 、R₂ 、R₃ 及R₄ 分別獨立地為氫或碳數1以上且30以下的有機基或具有乙烯性雙鍵之碳數1以上且30以下的有機基，n為0、1或2。[化2]

In the general formula (A1), R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or an organic group having from 1 to 30 carbon atoms or an organic group having an ethylenic double bond with carbon numbers of 1 to 30 or less. Base, n is 0, 1, or 2.

式(B1)中，R₅ 為碳數1以上且30以下的有機基或具有乙烯性雙鍵之碳數1以上且30以下的有機基。[化3]

In the formula (B1), R ₅ is an organic group having a carbon number of 1 or more and 30 or less or an organic group having an ethylenic double bond having a carbon number of 1 or more and 30 or less.

式(B2)中，R₆ 及R₇ 分別獨立地為碳數1以上且30以下的有機基或具有乙烯性雙鍵之碳數1以上且30以下的有機基。[化4]

In the formula (B2), R ₆ and R ₇ are each independently an organic group having a carbon number of 1 or more and 30 or less or an organic group having an ethylenic double bond having a carbon number of 1 or more and 30 or less.

[化5]

[化6]

[化7]

式(B6)中，R₈ 為碳數1以上且30以下的有機基或具有乙烯性雙鍵之碳數1以上且30以下的有機基。 其中，該式(1)中所包含之由該式(A1)表示之構造單元及由該式(B1)～(B6)表示之構造單元中的至少一個含有具有乙烯性雙鍵之碳數1以上且30以下的有機基。[化8]

In the formula (B6), R ₈ is an organic group having a carbon number of 1 or more and 30 or less or an organic group having an ethylenic double bond having a carbon number of 1 or more and 30 or less. Wherein, at least one of the structural unit represented by the formula (A1) and the structural unit represented by the formulas (B1) to (B6) contained in the formula (1) contains a carbon number 1 having an ethylenic double bond Above and 30 or less organic groups.

Furthermore, according to the present invention, there is provided a resin film composed of a cured film of the above-mentioned photosensitive resin composition.

Furthermore, according to the present invention, an electronic device provided with the above-mentioned resin film is provided. (Effects of the invention)

According to the present invention, there is provided a photosensitive resin composition whose cured product has excellent transparency, a resin film composed of a cured product of the photosensitive resin composition, and an electronic device provided with the resin film as a permanent film.

Hereinafter, an embodiment of the present invention will be described.

The term "electronic device" in this specification includes semiconductor chips, semiconductor components, printed wiring boards, circuit display devices, information communication terminals, light-emitting diodes, physical batteries, chemical batteries, and other components that apply electronic engineering technology. , Equipment, final product, etc.

(Photosensitive resin composition) First, the photosensitive resin composition of this embodiment will be described. The photosensitive resin composition of this embodiment contains a copolymer represented by general formula (1), a crosslinking agent, and a photosensitizer.

上述通式(1)中， l及m分別表示共聚物中的A及B的莫耳含有率， l+m=1， X為氫或碳數1以上且30以下的有機基， Y為-SR_5a ，R_5a 為碳數1以上且30以下的有機基， A包含由以下式(A1)表示之構造單元， B包含由式(B1)～(B6)表示之構造單元中的至少1個。[化9]

In the above general formula (1), l and m respectively represent the molar content of A and B in the copolymer, l+m=1, X is hydrogen or an organic group having 1 to 30 carbon atoms, and Y is- SR _5a , R _5a is an organic group with a carbon number of 1 or more and 30 or less, A contains the structural unit represented by the following formula (A1), and B contains at least one of the structural units represented by the formula (B1) to (B6) .

式(A1)中，R₁ 、R₂ 、R₃ 及R₄ 分別獨立地為氫或碳數1以上且30以下的有機基或具有乙烯性雙鍵之碳數1以上且30以下的有機基，n為0、1或2。[化10]

In formula (A1), R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or an organic group having 1 to 30 carbon atoms or an organic group having an ethylenic double bond having 1 to 30 carbon atoms , N is 0, 1, or 2.

式(B1)中，R₅ 為碳數1以上且30以下的有機基或具有乙烯性雙鍵之碳數1以上且30以下的有機基。[化11]

In the formula (B1), R ₅ is an organic group having a carbon number of 1 or more and 30 or less or an organic group having an ethylenic double bond having a carbon number of 1 or more and 30 or less.

式(B2)中，R₆ 及R₇ 分別獨立地為碳數1以上且30以下的有機基或具有乙烯性雙鍵之碳數1以上且30以下的有機基。[化12]

In the formula (B2), R ₆ and R ₇ are each independently an organic group having a carbon number of 1 or more and 30 or less or an organic group having an ethylenic double bond having a carbon number of 1 or more and 30 or less.

[化13]

[化14]

[化15]

式(B6)中，R₈ 為碳數1以上且30以下的有機基或具有乙烯性雙鍵之碳數1以上且30以下的有機基。 其中，通式(1)中所包含之由式(A1)表示之構造單元及由前述式(B1)～(B6)表示之構造單元中的至少一個含有具有乙烯性雙鍵之碳數1以上且30以下的有機基。換言之，本實施形態的共聚物含有具有乙烯性雙鍵之碳數1以上且30以下的有機基之構造單元作為必要成分。[化16]

In the formula (B6), R ₈ is an organic group having a carbon number of 1 or more and 30 or less or an organic group having an ethylenic double bond having a carbon number of 1 or more and 30 or less. Among them, at least one of the structural unit represented by the formula (A1) and the structural unit represented by the aforementioned formulas (B1) to (B6) contained in the general formula (1) contains a carbon number of 1 or more with an ethylenic double bond And 30 or less organic groups. In other words, the copolymer of this embodiment contains, as an essential component, a structural unit of an organic group having an ethylenic double bond having a carbon number of 1 or more and 30 or less.

The photosensitive resin composition of this embodiment contains the above-mentioned copolymer, and has various characteristics required for the photosensitive resin composition such as adhesion to the support, resolution, and heat resistance, and the cured product has excellent transparency It does not cause coloration or turbidity due to use in a high temperature environment, and maintains transparency.

Conventionally, as a photosensitive resin composition applied to the photolithography method, a composition containing a copolymer obtained by polymerizing a cyclic olefin monomer and a plurality of monomers including maleic anhydride is known. However, this conventional photosensitive resin composition has functions as a photosensitive material such as alkali solubility, processability, heat resistance, etc., but the resin film obtained by curing the composition may be colored. The inventors found that the cause of the coloration of the cured product is due to the structural unit derived from maleic anhydride in the copolymer. The copolymer used in this embodiment contains a structural unit derived from norbornene monomer or maleic anhydride containing an organic group having an ethylenic double bond with a carbon number of 1 or more and 30 or less, and has -SR at its end _5a group (S represents a sulfur atom). By using a copolymer with this structure, it is possible to obtain functions as a photosensitive material with alkali solubility, processability, heat resistance, etc., and the cured product has high transparency, and is caused by heat treatment or use in a high-temperature environment The decrease in transparency has been reduced, that is, a photosensitive resin composition having excellent heat discoloration resistance.

Hereinafter, each component constituting the photosensitive resin composition of this embodiment will be described.

＜Copolymer＞ The copolymer used in the photosensitive resin composition of this embodiment has a structure represented by general formula (1).

上述通式(1)中， l及m分別表示共聚物中的A及B的莫耳含有率， l+m=1， X為氫或碳數1以上且30以下的有機基， Y為-SR_5a ，S表示硫原子，R_5a 為碳數1以上且30以下的有機基， A包含由以下式(A1)表示之構造單元， B包含由式(B1)～(B6)表示之構造單元中的至少1個。[化17]

In the above general formula (1), l and m respectively represent the molar content of A and B in the copolymer, l+m=1, X is hydrogen or an organic group having 1 to 30 carbon atoms, and Y is- SR _5a , S represents a sulfur atom, R _5a is an organic group with a carbon number of 1 or more and 30 or less, A contains the structural unit represented by the following formula (A1), and B contains the structural unit represented by the formula (B1) to (B6) At least 1 of them.

The arrangement of the structural units A and B in the above copolymer is not limited, and the form of a random copolymer, a cross copolymer, a block copolymer, and a periodic copolymer can be adopted.

The composition ratio of the structural unit A and the structural unit B in the above-mentioned copolymer will be described. In the copolymer, the molar content (mol%) of the structural unit of A is set to 1, and the molar content (mol%) of the structural unit of B is set to m, and set to 1+m= In the case of 1, for example, the numerical range of l is preferably 0.1≦l≦0.9. In addition, the numerical range of m is preferably 0.1≦m≦0.9.

The structural unit A includes a structural unit derived from a norbornene monomer represented by the formula (A1).

[化18]

In formula (A1), R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or an organic group having 1 to 30 carbon atoms or an organic group having an ethylenic double bond having 1 to 30 carbon atoms , N is 0, 1, or 2.

The organic groups with 1 to 30 carbons or the organic groups with 1 to 30 carbons and an ethylenic double bond _{constituting R 1} to R _{4 in} the above general formula (A1) may be independently in its structure Contains one or more atoms selected from O (oxygen atom), N (nitrogen atom), S (sulfur atom), P (phosphorus atom), and Si (silicon atom). Furthermore, in this embodiment, _{all of the organic groups constituting R 1} , R ₂ , R ₃ and R ₄ can be those that do not have an acidic functional group. Thereby, the acid value in the copolymer can be easily controlled.

_{In this embodiment, R 1} to R ₄ in the above formula (A1) are each independently hydrogen or an organic group having 1 to 30 carbons or an organic group having an ethylenic double bond with 1 to 30 carbons. The group is preferably hydrogen or an organic group with a carbon number of 1 to 15 or an organic group with an ethylenic double bond having a carbon number of from 1 to 15 and more preferably hydrogen or an organic group with a carbon number of from 1 to 10 Or an organic group with a carbon number of 1 or more and 10 or less having an ethylenic double bond.

In this embodiment, examples of the organic group having 1 to 30 carbon atoms include alkyl, alkenyl, alkynyl, alkylene, aryl, aralkyl, alkaryl, and cycloalkyl groups. , Alkoxy and heterocyclyl. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, neopentyl, hexyl, Heptyl, octyl, nonyl and decyl. Examples of alkenyl groups include allyl groups, pentenyl groups, and vinyl groups. As an alkynyl group, an ethynyl group can be mentioned. As an alkylene group, a methylene group and an ethylene group are mentioned, for example. Examples of the aryl group include tolyl, xylyl, phenyl, naphthyl, and anthracenyl. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkaryl group include tolyl and xylyl. Examples of cycloalkyl groups include adamantyl groups, cyclopentyl groups, cyclohexyl groups, and cyclooctyl groups. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, secondary butoxy, isobutoxy, and tertiary butoxy, N-pentyloxy, neopentyloxy, n-hexyloxy. As a heterocyclic group, an epoxy group and an oxetanyl group are mentioned, for example.

As specific examples of the organic group having an ethylenic double bond with a carbon number of 1 or more and 30 or less, allyl group, acryloyl group, methacryloyl group, maleimino group, such as styryl group, Indenyl-like aromatic vinyl, etc.

In this embodiment, n in the above formula (A1) is 0, 1, or 2, and may be 0 or 1, or may be 0.

The structural unit B includes at least one of the structural units represented by formulas (B1) to (B6).

式(B1)中，R₅ 為碳數1以上且30以下的有機基或具有乙烯性雙鍵之碳數1以上且30以下的有機基。[化19]

In the formula (B1), R ₅ is an organic group having a carbon number of 1 or more and 30 or less or an organic group having an ethylenic double bond having a carbon number of 1 or more and 30 or less.

式(B2)中，R₆ 及R₇ 分別獨立地為碳數1以上且30以下的有機基或具有乙烯性雙鍵之碳數1以上且30以下的有機基。[化20]

In the formula (B2), R ₆ and R ₇ are each independently an organic group having a carbon number of 1 or more and 30 or less or an organic group having an ethylenic double bond having a carbon number of 1 or more and 30 or less.

[化21]

[化22]

[化23]

式(B6)中，R₈ 為碳數1以上且30以下的有機基或具有乙烯性雙鍵之碳數1以上且30以下的有機基。[化24]

In the formula (B6), R ₈ is an organic group having a carbon number of 1 or more and 30 or less or an organic group having an ethylenic double bond having a carbon number of 1 or more and 30 or less.

An organic group having 1 to 30 carbon atoms or an ethylenic double bond of _{R 5} to R _{8 in} the above general formula (B1), general formula (B2) and general formula (B6) has a carbon number of 1 or more and 30 The following organic groups may include one or more atoms selected from O, N, S, P, and Si in their structure. Furthermore, in the present embodiment, _{all of the organic groups constituting R 5} to R ₈ can be those that do not have an acidic functional group such as a carboxyl group. Thereby, the acid value in the copolymer can be easily controlled.

_{In this embodiment, R 5} to R ₈ in the general formula (B1), general formula (B2), and general formula (B6) are each independently an organic group having 1 to 30 carbon atoms or an ethylenic double The organic group having 1 to 30 carbon atoms in the bond is preferably an organic group having 1 to 15 carbon atoms or an organic group having an ethylenic double bond having 1 to 15 carbon atoms, and more preferably a carbon number of 1 An organic group above and below 10 or an organic group having an ethylenic double bond with a carbon number of 1 or more and 10 or less, more preferably an organic group with a carbon number of 1 to 6 or less, or an ethylenic double bond with a carbon number of 1 or more And 6 or less organic groups.

_{In this embodiment, as the organic group constituting R 5} to R _{8 in} the above formula (B1), formula (B2) and formula (B6), for example, alkyl, alkenyl, alkynyl, and alkylene groups Group, aryl group, aralkyl group, alkaryl group, cycloalkyl group, alkoxy group and heterocyclic group. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, neopentyl, hexyl, Heptyl, octyl, nonyl and decyl. Examples of alkenyl groups include allyl groups, pentenyl groups, and vinyl groups. As an alkynyl group, an ethynyl group can be mentioned. As an alkylene group, a methylene group and an ethylene group are mentioned, for example. Examples of the aryl group include tolyl, xylyl, phenyl, naphthyl, and anthracenyl. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkaryl group include tolyl and xylyl. Examples of cycloalkyl groups include adamantyl groups, cyclopentyl groups, cyclohexyl groups, and cyclooctyl groups. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, secondary butoxy, isobutoxy, tertiary butoxy, N-pentyloxy, neopentyloxy and n-hexyloxy. As a heterocyclic group, an epoxy group and an oxetanyl group are mentioned, for example. In this embodiment, as a specific example of an organic group having an ethylenic double bond of _{R 5} to R _{8 in} the above formula (B1), formula (B2), and formula (B6), the carbon number is 1 or more and 30 or less Examples include allyl groups, acryloyl groups, methacryloyl groups, maleimido groups, and aromatic vinyl groups such as styryl and indenyl groups.

In this embodiment, at least one of the structural unit represented by the aforementioned formula (A1) and the structural unit represented by the aforementioned formulas (B1) to (B6) contained in the formula (1) contains an ethylenic double bond An organic group having 1 to 30 carbon atoms.

In the copolymer represented by the above formula (1), X is hydrogen or an organic group having a carbon number of 1 or more and 30 or less. The organic group having a carbon number of 1 or more and 30 or less is the same as the organic group having a carbon number of 1 or more and 30 or less constituting the above-mentioned R ₁ to R ₄ or R ₅ to R _8.

In the copolymer represented by the above general formula (1), Y _{is a group represented by -SR 5a} , S is a sulfur atom, and R _5a is an organic group having 1 to 30 carbon atoms. The organic group having a carbon number of 1 or more and 30 or less may include one or more atoms selected from O, N, S, P, and Si. Examples of the organic group having 1 to 30 carbon atoms constituting R _5a include alkyl, alkenyl, alkynyl, alkylene, aryl, aralkyl, alkaryl, cycloalkyl, and alkane groups. Oxy and heterocyclic groups. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, neopentyl, hexyl, Heptyl, octyl, nonyl and decyl. Examples of alkenyl groups include allyl groups, pentenyl groups, and vinyl groups. As an alkynyl group, an ethynyl group can be mentioned. As an alkylene group, a methylene group and an ethylene group are mentioned, for example. Examples of the aryl group include tolyl, xylyl, phenyl, naphthyl, and anthracenyl. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkaryl group include tolyl and xylyl. Examples of cycloalkyl groups include adamantyl groups, cyclopentyl groups, cyclohexyl groups, and cyclooctyl groups. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, secondary butoxy, isobutoxy, tertiary butoxy, N-pentyloxy, neopentyloxy and n-hexyloxy. As a heterocyclic group, an epoxy group and an oxetanyl group are mentioned, for example.

Y may contain a structural unit derived from a radical polymerization initiator, hydrogen or a structural unit derived from a chain transfer agent, or it may be a structural unit derived from a radical polymerization initiator, hydrogen or a structure derived from a chain transfer agent unit. This is because when synthesizing the copolymer represented by the above general formula (1), in the case of using a radical polymerization initiator as a polymerization initiator, it is possible to stop the reaction as a radical chain reaction of the polymerization reaction. Form Y.

The structure of Y derived from the chain transfer agent is -SR _5a . Here, S represents a sulfur atom, and R _5a is a linear or branched hydrocarbon group having 1 to 15 carbons or an organic group having 1 to 15 carbons. -SR _5a can be introduced into the copolymer of formula (1) using the following compounds: compounds represented by formula (Y1-a) or formula (Y2-a); 1-butanethiol, 1-octanethiol, 1 -Alkyl mercaptans such as decyl mercaptan; thiocarboxylic acids such as thioglycolic acid and 3-mercaptopropionic acid; ethyl mercaptoacetate, 2-ethylhexyl thioglycolate, 2-ethylhexyl 3-mercaptopropionate, etc. Thiocarboxylic acid esters; polythiols such as trimethylolpropane tris(3-mercaptopropionate), etc.

[化25]

[化26]

For example, in the case where the compound represented by the above formula (Y1-a) is used as a chain transfer agent to produce a copolymer, a copolymer in which Y in the formula (1) is a structure represented by the formula (Y1) can be obtained. In addition, when the compound represented by the above formula (Y2-a) is used as a chain transfer agent to produce a copolymer, a copolymer in which Y in the formula (1) is a structure represented by the formula (Y2) can be obtained.

[化27]

In this embodiment, from the viewpoint of forming a suitable crosslinked structure, the lower limit of the Mw (weight average molecular weight) of the copolymer may be, for example, 1500 or more, or 2000 or more, preferably 2500 or more, and more preferably Above 3000. In addition, from the same viewpoint as the lower limit, the upper limit of the Mw of the copolymer may be, for example, 30,000 or less, preferably 25,000 or less, and more preferably 20,000 or less.

In addition, from the viewpoint of making the physical properties of each molecular chain of the copolymer uniform and making the shape of the resin film composed of the photosensitive resin composition containing the copolymer good, the polydispersity of the copolymer of this embodiment The upper limit of the degree is, for example, 2.5 or less, preferably 2.2 or less, more preferably 2.0 or less, and still more preferably 1.5 or less. In addition, from the same viewpoint as the upper limit, the lower limit of the polydispersity of the copolymer is preferably 1.0 or more, for example. In addition, the polydispersity is represented by Mw (weight average molecular weight)/Mn (number average molecular weight), and refers to the dispersion degree representing the width of the molecular weight distribution.

In addition, the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw/Mn) use, for example, polystyrene conversion values obtained from a calibration curve of standard polystyrene (PS) obtained by GPC measurement . The measurement conditions are, for example, as follows. Device: Gel Permeation Chromatography Device HLC-8320GPC manufactured by TOSOH CORPORATION Column: TSK-GEL Supermultipore HZ-M manufactured by TOSOH CORPORATION Detector: RI detector for liquid chromatography Measuring temperature: 40℃ Solvent: THF Sample concentration: 2.0mg/ml

Regarding the copolymer of the present embodiment, for example, in a molecular weight distribution curve obtained by GPC (Gel Permeation Chromatography), the peak area with a molecular weight of 1000 or less can be set to 1% or less of the whole. In this way, by setting the ratio of the peak area of the molecular weight of the molecular weight distribution curve obtained by GPC to 1000 or less within the above range, the pattern shape of the film composed of the resin composition containing the copolymer can be improved. Therefore, regarding the liquid crystal display device and the solid-state imaging element including the film as a permanent film, the operation reliability can be improved. In addition, the lower limit of the amount of the low molecular weight component in the copolymer is not limited. However, the copolymer of this embodiment allows the case where the peak area with a molecular weight of 1000 or less in the molecular weight distribution curve obtained by GPC is 0.01% or more of the whole. In addition, the amount of low-molecular-weight components in the copolymer is calculated from the ratio of the total area of components corresponding to molecular weights of 1,000 or less to the area of the entire molecular weight distribution based on the data related to the molecular weight obtained by GPC measurement, for example.

The alkali dissolution rate of the copolymer in this embodiment is, for example, 300 Å/sec or more and 20,000 Å/sec or less, and more preferably 500 Å/sec or more and 25,000 Å/sec or less. In addition, the alkali dissolution rate of the copolymer in this embodiment is, for example, 20,000 Å/sec or less. The alkali dissolution rate of the copolymer is calculated, for example, by the following method: The copolymer solution obtained by dissolving the copolymer in propylene glycol monomethyl ether acetate and adjusting the solid content to 20% by weight is applied to the silicon by spin coating. On the wafer, soft-baked it at 110°C for 100 seconds to obtain a copolymer film. The obtained copolymer film was immersed in a 2.38% tetramethylammonium hydroxide aqueous solution at 23°C, and the measurement was visually The time until the aforementioned copolymer film disappears.

By setting the alkali dissolution rate of the copolymer to be equal to or higher than the above lower limit, the throughput in the development step using the alkali developer can be improved. In addition, by setting the alkali dissolution rate of the copolymer to be equal to or less than the above upper limit, the residual film rate after the development step using the alkali developer can be increased. Therefore, the film reduction caused by the lithography step can be suppressed.

(Manufacturing method of copolymer) The copolymer of this embodiment is prepared, for example, by the following method: a copolymer is produced by polymerizing monomers in a polymerization step, and then a low molecular weight component is removed by a low molecular weight component removal step to obtain a copolymer as the main component的copolymer. This will be described in detail below.

(Polymerization step) Prepare norbornene-type monomer (A) and 1 species selected from the group consisting of maleic anhydride (B), maleimine (C) and maleimine derivatives (D) the above. In addition, the norbornene-type monomer may be prepared one type or two or more types. In the copolymer represented by the above general formula (1), the structural unit A is derived from a norbornene-type monomer (A), and the structural unit B is derived from maleic anhydride (B), maleimide (C) or Maleimine derivative (D). [化28]

As the norbornene-type monomer represented by the formula (A), specifically, bicyclo[2.2.1]-hept-2-ene (common name: 2-norbornene) can be mentioned, and more specifically , Examples of those having an alkyl group include 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, and 5-hexyl-2-norbornene. Camphene, 5-decyl-2-norbornene, etc. Examples of those having an alkenyl group include 5-allyl-2-norbornene and 5-(2-propenyl)-2-norbornene , 5-(1-methyl-4-pentenyl)-2-norbornene, etc., as those having an alkynyl group, 5-ethynyl-2-norbornene, etc., as those having an aralkyl group , For example, 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene and the like. In addition, as a norbornene-type monomer, _{the structure of the group of R 1} , R ₂ , R ₃ , and R ₄ in formula (A) containing the above-mentioned ethylenic double bond with carbon number of 1 to 30 can be used. The following organic base.

Next, in the presence of the above-mentioned chain transfer agent, the monomer represented by the formula (A), the monomer represented by the formula (B), the monomer represented by the formula (C), or the monomer represented by the formula (D) The monomer undergoes addition polymerization. Here, a copolymer of these monomers (copolymer 1) is formed by radical polymerization.

As the polymerization method, for example, a method of performing polymerization using a radical polymerization initiator and a molecular weight regulator as required is suitable. In this case, methods such as suspension polymerization, solution polymerization, dispersion polymerization, and emulsion polymerization can be used. Among them, solution polymerization is preferred. In the solution polymerization, the total amount of each monomer may be charged at once, or a part of the monomer may be charged into the reaction vessel and the remaining part may be added dropwise.

For example, the monomer represented by the formula (A), the monomer represented by the formula (B), the monomer represented by the formula (C), the monomer represented by the formula (D) and the polymerization initiator are dissolved in a solvent After that, heating is performed for a predetermined time, whereby the norbornene-type monomer represented by the formula (A), maleic anhydride, and maleimine are subjected to solution polymerization. The heating temperature is, for example, 50 to 80°C, and the heating time is 10 to 20 hours.

As a solvent used for polymerization, diethyl ether, tetrahydrofuran, toluene, methyl ethyl ketone, ethyl acetate, etc. are mentioned, for example, Any one or more of these can be used.

As a radical polymerization initiator, an azo compound, an organic peroxide, etc. are mentioned, Any one or more of these can be used. As the azo compound, for example, azobisisobutyronitrile (AIBN), 2,2'-azobis(2-methylpropionic acid) dimethyl ester, 1,1'-azobis(cyclo Capronitrile) (ABCN), any one or more of these can be used. Also, as organic peroxides, for example, hydrogen peroxide, di-tertiary butyl peroxide (DTBP), benzoyl peroxide (BPO), and methyl ethyl ketone peroxide (MEKP) can be cited. , Any one or more of these can be used.

The amount (number of moles) of the radical polymerization initiator is preferably set to 1 mol% to 10 mol% with respect to the total amount of monomers used. By appropriately setting the amount of the polymerization initiator within the aforementioned range, and appropriately setting the reaction temperature and reaction time, the weight average molecular weight (Mw) of the obtained copolymer can be adjusted to 5,000 to 30,000.

By this polymerization step, it is possible to have a structural unit represented by the following formula (A1), a structural unit represented by the following formula (B3), a structural unit represented by the following formula (B5), and a structural unit represented by the following formula ( B6) represents the polymerization of copolymer 1 of the structural unit. Among them, in the copolymer 1, R ₁ of the structure of formula (A1) is preferably the same in each repeating unit, and may be different for each repeating unit. The same applies to R ₂ to R ₄ and R ₈ .

[化29]

[化30]

[化31]

[化32]

In formula (1), n, R ₁ to R ₄ and R ₈ are the same as defined above.

Copolymer 1 may be obtained by randomly disposing the above-mentioned structural units (A1), (B3), (B5), and (B6), or may be obtained by alternately disposing the structural units (A1), (B3), (B5) and (B6). In addition, the structural units (A1), (B3), (B5), and (B6) may be obtained by block copolymerization. From the viewpoint of obtaining uniform solubility of the photosensitive resin composition, the copolymer 1 is preferably an alternating copolymer.

(Low molecular weight component removal step) Next, a large amount of poor solvent, such as hexane and methanol, is added to the organic layer containing copolymer 1 and low molecular weight components such as residual monomers and oligomers, so that the reaction mixture containing copolymer 1 is solidified and precipitated. Here, as low molecular weight components, residual monomers, oligomers, polymerization initiators, and the like are included. Next, filtration is performed to dry the obtained coagulum. Thereby, it is possible to obtain a product containing copolymer 1 from which low-molecular-weight components have been removed as the main component (main product).

By reducing the amount of low-molecular-weight components in the copolymer, the film formed of the copolymer can suppress the deformation of the pattern during curing, and the pattern shape of the film formed of the photosensitive resin composition containing the copolymer can be made Become good. Regarding a liquid crystal display device and a solid-state imaging element including the film as a permanent film, the operation reliability can be improved.

(Open loop step) Next, it is possible to open a ring of a part of the structural unit derived from maleic anhydride (B3) of the obtained copolymer 1 while making the remaining part of the repeating unit ring closed. With this, it is possible to introduce a radical polymerizable group while adjusting the amount of carboxyl groups in the copolymer 1. In this embodiment, it is preferable to open the ring of, for example, 10% or more of the repeating units in the structural unit (B3) derived from maleic anhydride of the copolymer 1. Among these, 15% or more of the repeating units of the total number of repeating units derived from the cyclic structure of maleic anhydride in the copolymer 1 are preferably ring-opened. Furthermore, in this embodiment, it is preferable to open the ring of 60% or less of the repeating units derived from maleic anhydride in the copolymer 1, and it is more preferable to open the ring of 50% or less of the repeating units. By setting it as the said range, it becomes easy to provide sufficient alkali developer to the copolymer 1, and it becomes easy to perform the crosslinking reaction by a photoradical generator more efficiently.

In this ring opening step, _{an alcohol represented by R 5} -OH (wherein R ₅ is the same as above) or water is allowed to act on the structural unit derived from maleic anhydride, so that the structural unit represented by the above formula (B3) is The acid anhydride site opens the ring to generate carboxyl group or its salt in the precursor polymer.

In this step, when alcohol is allowed to function, a structural unit represented by the following formula (B1) is generated in the copolymer, for example.

式(B1)中，R₅ 為碳數1以上且30以下的有機基或具有乙烯性雙鍵之碳數1以上且30以下的有機基。 又，有時還形成由式(B2)表示之構造體。[化33]

In the formula (B1), R ₅ is an organic group having a carbon number of 1 or more and 30 or less or an organic group having an ethylenic double bond having a carbon number of 1 or more and 30 or less. In addition, a structure represented by formula (B2) may be formed.

式(B2)中，R₆ 及R₇ 分別獨立地為碳數1以上且30以下的有機基或具有乙烯性雙鍵之碳數1以上且30以下的有機基。[化34]

In the formula (B2), R ₆ and R ₇ are each independently an organic group having a carbon number of 1 or more and 30 or less or an organic group having an ethylenic double bond having a carbon number of 1 or more and 30 or less.

When water is applied to the copolymer 1, a structural unit represented by the following formula (B4) is generated in the precursor polymer.

[化35]

This step can be performed, for example, by adding a predetermined amount of alcohol or water to a solution containing the copolymer 1, and heating it.

The alcohol is preferably a monohydric alcohol. Can be set to an alcohol R ₅ OH, R ₅ is an organic group of the person can be used. As the alcohol, for example, allyl alcohol, methallyl alcohol, 3-buten-1-ol, 3-methyl-3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol, 6-hepten-1-ol, 7-octene-1-ol, 8-nonen-1-ol, 9-decen-1-ol, 10-undecene -1-ol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxy methacrylate Butyl ester, 1,4-cyclohexanedimethanol monoacrylate, and 1,4-cyclohexanedimethanol monomethacrylate, any one or more of these can be used.

The solvent for dissolving the precursor polymer can be appropriately selected from those that do not hinder the reaction, and as the heating condition, for example, it can be set in the range of 50 to 100°C. The reaction time can be appropriately set while observing the degree of change in the chemical structure of the polymer, etc. In addition, as the solvent used in this step, for example, as a highly versatile solvent, diethyl ether, tetrahydrofuran, toluene, methyl ethyl ketone, ethyl acetate, etc. can be cited, and any one of these can be used the above.

In this heating, from the viewpoint of promoting the reaction, a catalyst can be appropriately added, for example, an alkali catalyst or an acid catalyst can be added. As the alkali catalyst, alkylamines such as pyridine and triethylamine, amine compounds such as dimethylaniline, eulotropine, and dimethylaminopyridine, and metal salts such as sodium acetate can be used. In addition, as the acid catalyst, inorganic acids such as sulfuric acid and hydrochloric acid, organic acids such as p-toluenesulfonic acid, Lewis acids such as boron trifluoride ether and the like can be used.

The copolymer obtained according to this embodiment can be ideally used to form a photosensitive resin film due to the specificity of the chemical properties contained in its structural unit. In addition, in this specification, the "photosensitive resin film" refers to a resin film used in an exposure step in the production process of an electronic device or the like. For example, "photosensitive resin film" refers to the part irradiated with light that hardens. On the other hand, the part that is not irradiated is dissolved in a developing solution (for example, an alkaline solution) and removed during the development step. membrane.

＜Crosslinking agent＞ In this embodiment, the crosslinking agent is not limited as long as it is a compound containing a functional group that reacts with the active hydrogen of the copolymer. As the functional group that reacts with the active hydrogen of the copolymer, for example, it preferably contains at least one selected from the group consisting of glycidyl, oxetanyl and blocked isocyanate groups, and more preferably contains epoxy The propyl group or oxetanyl group further preferably contains a glycidyl group. Thereby, a suitable cross-linked structure can be formed. Moreover, the photosensitive resin composition can use together 1 type(s) or 2 or more types selected from the compound which has a blocked isocyanate group, an epoxy compound, and an oxetane compound.

As a compound having a glycidyl group that can be used as a crosslinking agent, for example, allyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and neopentyl glycidyl ether can be used. Glycidyl ethers such as alcohol diglycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether, glycidyl ether of bisphenol A (or F), adipic acid two Glycidyl esters such as glycidyl ester and diglycidyl phthalate, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate, 3,4-ring Oxy-6-methylcyclohexylmethyl (3,4-epoxy-6-methylcyclohexane) carboxylate, bis(3,4-epoxy-6-methylcyclohexylmethyl)hexanedi Ester, dicyclopentadiene oxide, bis(2,3-epoxycyclopentyl) ether, CELLOXIDE 2021, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, CELLOXIDE 8000, EPORIDE GT401, etc. manufactured by Daicel Chemical Industries Ltd. Alicyclic epoxy, 2,2'-(((((1-(4-(2-(4-(oxiran-2-ylmethoxy)phenyl)propan-2-yl)benzene Yl)ethane-1,1-diyl)bis(4,1-phenylene))bis(oxy))bis(methylene))bis(ethylene oxide) (for example, Techmore VG3101L(Printec Corporation)), EPOLITE 100MF (manufactured by KYOEISHA CHEMICAL Co., LTD.), EPIOL TMP (manufactured by NOF CORPORATION), 1,4-cyclohexanedimethanol diglycidyl ether (New Japan Chemical Co., Ltd.) . Manufacturing, SHOWA DENKO KK manufacturing, etc.) and other aliphatic glycidyl ethers, 3,3',5,5'-tetramethyl-4,4'-bis(glycidoxy)-1,1' -Aromatic glycidyl ether such as biphenyl, 1,1,3,3,5,5-hexamethyl-1,5-bis(3-(oxiran-2-ylmethoxy)propane Base) trisiloxane (for example, DMS-E09 (manufactured by Gelest, Inc.)) and other epoxy resins.

Also, for example, LX-01 (manufactured by DAISO CHEMICAL CO., LTD.), jER1001, jER1002, jER1003, jER1004, jER1007, jER1009, jER1010, jER828, jER825 (trade name; manufactured by Mitsubishi Chemical Corporation.) can also be used. Phenol A type epoxy resin, bisphenol F type epoxy resin such as jER807 (trade name; manufactured by Mitsubishi Chemical Corporation.), jER152, jER154 (trade name; manufactured by Mitsubishi Chemical Corporation.), EPPN201, EPPN202 (trade name; Nippon Kayaku) Co., Ltd.) and other phenol novolac type epoxy resins, EOCN102, EOCN103S, EOCN104S, 1020, 1025, 1027 (trade name; manufactured by Nippon Kayaku Co., Ltd.), jER157S70 (trade name; Mitsubishi Chemical Corporation. Manufacture) and other cresol novolac type epoxy resins, Araldite CY179, Araldite CY184 (trade name; manufactured by Huntsman Advanced Materials), ERL-4206, 4221, 4234, 4299 (trade name; manufactured by The Dow Chemical Company), EPICLON 200 , EPICLON400 (trade name; manufactured by DIC CORPORATION), jER871, jER872 (trade name; manufactured by Mitsubishi Chemical Corporation.) and other cycloaliphatic epoxy resins, poly[(2-oxiranyl)-1,2-ring Hexanediol]2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether (Poly[(2-oxiranyl)-1,2-cyclohexanediol]2-ethyl-2-(hydroxymethyl)-1, Multifunctional alicyclic epoxy resins such as 3-propanediol ether) (3:1), EHPE-3150 (manufactured by Daicel Corporation). The photosensitive resin composition can contain one type or two or more types of epoxy compounds exemplified above.

As a compound having an oxetanyl group that can be used as a crosslinking agent, for example, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl} Benzene, bis[1-ethyl(3-oxetanyl)] methyl ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl , 4,4'-bis (3-ethyl-3-oxetanyl methoxy) biphenyl, ethylene glycol bis (3-ethyl-3-oxetanyl methyl) ether, diethylene glycol bis (3-Ethyl-3-oxetanylmethyl)ether, bis(3-ethyl-3-oxetanylmethyl)diphenolate, trimethylolpropane tris(3-ethyl-3- Oxetanyl methyl) ether, neopentyl erythritol tetrakis (3-ethyl-3-oxetanyl methyl) ether, poly[[3-[(3-ethyl-3-oxetanyl) methyl) Oxy]propyl]silsesquioxane] derivatives, oxetanyl silicate, phenol novolac type oxetane, 1,3-bis[(3-ethyloxetane-3- Yl)methoxy]benzene and other oxetane compounds. The photosensitive resin composition can contain one type or two or more types of the oxetane compounds exemplified above.

The compound having a blocked isocyanate group that can be used as a crosslinking agent is not limited, but for example, a compound in which the isocyanate group of a multifunctional isocyanate is protected by a blocking agent can be mentioned.

The above-mentioned polyfunctional isocyanate is an organic compound having a plurality of isocyanate groups in one molecule. As the above-mentioned polyfunctional isocyanate, for example, a group selected from 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2, 4-trimethyl-1,6-hexamethylene diisocyanate, lysine diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 1,3-bis(isocyanate methyl)-cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, Diisocyanate compounds such as xylol diisocyanate and stubborn diisocyanate; derivatives of the above-mentioned diisocyanate compounds such as isocyanurate-modified polyfunctional isocyanate, biuret-modified polyfunctional isocyanate, amine ester-modified polyfunctional isocyanate, etc. One or more of the others.

Examples of the above-mentioned blocking agent include selected from alcohol compounds, phenol compounds, active methylene compounds, thiol compounds, amide compounds, imine compounds, imidazole compounds, and urea compounds. One or two or more of compounds, oxime-based compounds, amine-based compounds, imine-based compounds, bisulfites, pyridine-based compounds, and the like.

Specific examples of the blocking agent include methanol, ethanol, propanol, butanol, 2-ethylhexanol, methyl siloxol, butyl siloxol, methyl carbitol, benzyl alcohol, and cyclohexyl alcohol. Alcohol compounds such as hexanol; phenolic compounds such as phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, hydroxybenzoate, etc.; dimethyl malonate , Diethyl malonate, methyl acetylacetate, ethyl acetate, acetone and other active methylene compounds; mercaptan compounds such as butane mercaptan and dodecyl mercaptan; acetaniline , Acetamide, ε-caprolactone, δ-valerolactamide, γ-butyrolactamide and other amide-based compounds; succinimide, maleimide and other amide-based compounds; imidazole, 2-methylimidazole and other imidazole compounds; urea, thiourea, ethylene urea and other urea compounds; formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime and other oxime compounds; diphenylamine Amine compounds such as aniline and carbazole; imine compounds such as ethyleneimine and polyethyleneimine; bisulfites such as sodium bisulfite; pyridine compounds such as 2-hydroxypyridine and 2-hydroxyquinoline.

As a compound having a blocked isocyanate group that can be used as a crosslinking agent, specifically, BURNOCK D-500 (blocked toluene diisocyanate) manufactured by Dainippon Printing Ink Manufacturing Co., Ltd., BURNOCK D -550 (blocked 1,6-hexamethylene diisocyanate), BURNOCK D-980K (blocked 1,6-hexamethylene diisocyanate); TAKENATE B manufactured by MITSUI TAKEDA CHEMICALS, INC. -830 (blocked toluene diisocyanate), TAKENATE B-815N (blocked 4,4'-methylene bis(cyclohexyl isocyanate)), TAKENATE B-842N (1,3-bis(isocyanate methyl) Base) cyclohexane blocked form), TAKENATE B-846N (1,3-bis(isocyanate methyl) cyclohexane blocked form), TAKENATE B-874N (isophorone diisocyanate blocked form ), TAKENATE B-882N (blocked 1,6-hexamethylene diisocyanate), TAKENATE B-890 (blocked diisocyanate); TAKENATE B-820NP (1,3-bis( Isocyanate methyl) cyclohexane blocked form), TAKENATE B-885N (1,6-hexamethylene diisocyanate blocked form); DURANATE MF-B60X (1,6-hexamethylene) manufactured by Asahi Kasei Corporation Blocked methyl diisocyanate), DURANATE MF-K60X (blocked 1,6-hexamethylene diisocyanate), etc. The photosensitive resin composition of this embodiment can contain 1 type or 2 or more types of these.

(Photosensitizer) When the photosensitive resin composition is a positive type, a photoactive compound can be used as the photosensitizer, for example, a quinone diazide compound can be used. For example, any one or more of the following compounds can be used.

[化36]

[化37]

n2為1以上且5以下的整數。[化38]

n2 is an integer of 1 or more and 5 or less.

[化39]

[化40]

[化41]

In each of the above compounds, Q is any one of the structures shown below or a hydrogen atom. However, at least one of Q in each compound is any one of the following. Among them, from the viewpoint of transparency and dielectric constant of the photosensitive resin composition, the o-naphthoquinone diazide sulfonic acid derivative of Q series (a) or (b) is preferred.

[化42]

In addition, in addition to the above-mentioned photoactive compound, the positive photosensitive resin composition may also include an acid generator that generates an acid by light or heat. By including this kind of acid generator, the photosensitive resin composition is exposed and developed, and then irradiated with light or heated, whereby the crosslinking reaction of the crosslinking agent can be promoted. At this time, the acid generator is preferably 3 parts by mass or less with respect to 100 parts by mass of the crosslinking agent. As a photoacid generator that generates acid by light, those described later can be used. As a thermal acid generator that generates acid by heat, aromatics such as SI-45L, SI-60L, SI-80L, SI-100L, SI-110L, SI-150L (manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD.) can be used Tribe salt. When the total solid content of the photosensitive resin composition is 100% by mass, the content of the thermal acid generator is preferably, for example, 0.1% by mass or more and 5% by mass or less. In addition, in the present embodiment, the total solid content of the photosensitive resin composition means components other than the solvent.

Moreover, when the photosensitive resin composition is a negative type, a photoacid generator can be used as a photosensitizer. As the photoacid generator, any one that absorbs light energy to generate Brunsted acid or Lewis acid may be used. For example, triphenyl sulfonate trifluoromethanesulfonate, trifluoromethanesulfonate tris(4-third (Butylphenyl) sulfonium salts and other sulfonium salts; diazonium salts such as p-nitrophenyldiazonium hexafluorophosphate; ammonium salts; phosphonium salts; diphenylphosphonium trifluoromethanesulfonate, tetrakis Fluorophenyl) boric acid (triisopropylphenyl) iodonium salts; diazomethanes such as quinonediazide and bis(phenylsulfonyl)diazomethane; 1-phenyl-1-(4 -Methylphenyl)sulfonyloxy-1-benzylmethane, N-hydroxynaphthalimide-trifluoromethanesulfonate and other sulfonic acid esters; diphenyldisulfonate and other sulfonates ; Tris(2,4,6-trichloromethyl)-symmetric tris, 2-(3,4-methylenedioxyphenyl)-4,6-bis-(trichloromethyl)-symmetry Three compounds such as three compounds. These photoacid generators can be used individually or in combination of multiple types.

In addition, when the photosensitive resin composition is of a negative type, as the second crosslinking agent, one that crosslinks the copolymer by the action of an acid may be included. The second crosslinking agent is one that crosslinks the copolymer using the acid generated by the photoacid generator as a catalyst, and is different from the compound used for the crosslinking agent. For example, a melamine type crosslinking agent, a urea type crosslinking agent, etc. are mentioned. As the melamine-based crosslinking agent, for example, hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine, etc. can be mentioned. Among them, hexamethoxymethyl melamine is preferred. Methyl melamine. As the urea-based crosslinking agent, for example, methylated urea resin, bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, bisbutoxymethylurea, etc. Among them, methylated urea resin is preferred. Examples of commercially available products of methylated urea resins include MX-270, MX-280, MX-290 (manufactured by Sanwa Chemical Co., LTD.) and the like.

When the total solid content of the resin composition is 100% by mass, the ratio of the second crosslinking agent in the negative photosensitive resin composition is preferably 5% by mass or more and 40% by mass or less, from the viewpoint of resolution , More preferably, it is 5 mass% or more and 30 mass% or less, More preferably, it is 10-25 mass %.

In the above-mentioned photosensitive resin composition, when the photosensitive resin composition is a positive type, the ratio of each component is, for example, as follows. When the total solid content of the photosensitive resin composition is 100% by mass, for example, it is preferable to contain 30% by mass or more and 70% by mass or less of the aforementioned copolymer, and among them, it is preferable to contain 40% by mass or more and 60% by mass. %the following. In addition, when the total solid content of the photosensitive resin composition is 100% by mass, for example, it is preferable to contain 15% by mass or more and 50% by mass or less of a crosslinking agent, and among these, it is preferable to contain 20% by mass or more and 50% by mass. Less than mass%. Furthermore, when the total solid content of the photosensitive resin composition is 100% by mass, for example, it is preferable to contain 5 mass% or more and 40 mass% or less of the photoactive compound as a photosensitizer, more preferably 10 mass%. Above and 30% by mass or less.

Moreover, when the photosensitive resin composition is a negative type, the ratio of each component is as follows, for example. When the total solid content of the photosensitive resin composition is 100% by mass, for example, it is preferable to contain 30% by mass or more and 70% by mass or less of the aforementioned copolymer, and among them, it is preferable to contain 40% by mass or more and 60% by mass. %the following. In addition, when the total solid content of the photosensitive resin composition is 100% by mass, for example, it is preferable to contain 15% by mass or more and 50% by mass or less of a crosslinking agent (except for the second crosslinking agent). It is preferable to contain 20% by mass or more and 50% by mass or less. Furthermore, when the total solid content of the photosensitive resin composition is 100% by mass, the amount of the photoacid generator is, for example, 0.1% by mass or more and 40% by mass or less, from the viewpoint that a high-resolution patterned film can be formed. More preferably, it is 1% by mass or more and 30% by mass or less.

Additives such as solvents, antioxidants, surfactants, adhesion aids, dissolution promoters, fillers, sensitizers, and polyphenols can also be added to the photosensitive resin composition. Hereinafter, the details of the representative components will be described.

(Solvent) The photosensitive resin composition described in this embodiment can be used as a varnish by dissolving the above-mentioned components in a solvent. Examples of such solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl Ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl -1,3-butanediol acetate, 1,3-butanediol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate and methyl-3-methoxypropionate, etc.

In the photosensitive resin composition of this embodiment, depending on the purpose and required characteristics of each application, fillers, binder resins other than the aforementioned polymers, crosslinking agents, acid generators, heat resistance improvers, and developing agents may be blended. Additives, plasticizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, matting agents, defoamers, leveling agents, antistatic agents, dispersants, slip agents, surface modifiers, thixotropic agents, thixotropic agents Additives, surfactants, silane-based, aluminum-based, titanium-based coupling agents, polyphenol compounds, and other components other than the above-mentioned essential components.

(Preparation of photosensitive resin composition) The method for preparing the photosensitive resin composition in this embodiment is not limited, and it can be prepared using a conventionally known method. For example, it can be prepared by mixing and dissolving the above-mentioned components in a solvent. Thereby, a photosensitive resin composition as a varnish can be obtained.

By making the photosensitive resin composition of this embodiment into a cured product, a resin film can be obtained. Such a resin film can be used as a resist, for example, and can also constitute a permanent film such as a protective film for an electronic device, an interlayer film, or a dam material, for example.

Regarding the photosensitive resin composition of the present embodiment, the transmittance of the resin film measured under the following conditions is preferably 95% or more, and more preferably 98% or more. (Conditions) The photosensitive resin composition is coated on a glass substrate, dried at 100°C for 120 seconds, and ^{exposed at an exposure amount of 300 mJ/cm 2} to obtain a resin film with a thickness of 3 μm A, the light transmittance of light with a wavelength of 400 nm was evaluated with a spectrophotometer, and set as the transmittance T _A % before the heat resistance test.

Regarding the photosensitive resin composition of the present embodiment, the heat discoloration resistance of the resin film measured under the following conditions is preferably 95% or more, more preferably 96% or more. (Conditions) The photosensitive resin composition is coated on a glass substrate, dried at 100°C for 120 seconds, and ^{exposed at an exposure amount of 300 mJ/cm 2} to obtain a resin film with a thickness of 3 μm A, the light transmittance of light with a wavelength of 400 nm was evaluated with a spectrophotometer, and set as the transmittance T _A % before the heat resistance test. Regarding the resin film B obtained by heating the resin film A at 250° C. for 1 hour in an atmospheric environment, the light transmittance of light having a wavelength of 400 nm was evaluated with a spectrophotometer, and it was set as the transmittance T _B % after the heat resistance test. Let T _B /T _A ×100 be the thermal discoloration resistance %. Since the permanent film obtained by curing the photosensitive resin composition of the present invention becomes a permanent film with excellent transmittance and heat discoloration resistance, it is particularly suitable for applications requiring transparency, especially those requiring no coloring even if heated. Coloring patterns, black matrix, protective layer, ribs and spacers of electronic devices with various display devices such as liquid crystal display devices and organic EL elements.

The embodiments of the present invention have been described above, but these are examples of the present invention, and various configurations other than the above can be used. [Example]

Hereinafter, the present invention will be described with examples and comparative examples, but the present invention is not limited to these.

(Synthesis example 1: Synthesis of precursor polymer A) In a reaction vessel equipped with a reflux cooling tube and a dropping funnel, a 75% toluene solution of 2-norbornene (NB, 98.1g, 73.6g, 0.782mol converted to 2-norbornene), maleic anhydride (MAN, 76.7) g, 0.782 mol) and 371.6 g of methyl ethyl ketone (MEK), stirred and dissolved. Next, after removing the dissolved oxygen in the system by bubbling with nitrogen, heating was performed, and when the internal temperature reached 80°C, dimethyl 2,2'-azobisisobutyrate ( Manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-601, 7.20g, 0.031mol) and neopentylerythritol tetrakis (3-mercaptopropionate) (PEMP, 15.3g, 0.029mol) dissolved in MEK31.5g In the solution. After that, the reaction was further carried out at 80°C for 7 hours. Next, the reaction mixture was cooled to room temperature. The reacted solution was poured into a large amount of methanol to precipitate a polymer. Next, the polymer was collected by filtration, washed with methanol, and then vacuum-dried at 120°C for 16 hours. The yield of the polymer was 145.3 g, and the yield was 97%. In addition, in the polymer, the weight average molecular weight Mw was 3,500, and the dispersion degree (weight average molecular weight Mw/number average molecular weight Mn) was 1.62.

(Synthesis example 2: Synthesis of precursor polymer B) In a reaction vessel equipped with a reflux cooling tube and a dropping funnel, a 75% toluene solution (54.8g, converted to 2-norbornene, 41.1g, 0.436mol) of 2-norbornene, V-601 (4.0g, 0.017mol) was added to a reaction vessel equipped with a reflux cooling tube and a dropping funnel. ) And MEK26.5g, stirred and dissolved. Next, after removing the dissolved oxygen in the system by bubbling with nitrogen, heating was performed, and when the internal temperature reached 60°C, N-cyclohexylmaleimide (CMI, 7.8g, 0.044mol), maleic anhydride (38.5g, 0.393mol) and 3-mercaptopropyltrimethoxysilane (trade name: KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd., 8.6g, 0.044mol) dissolved The solution obtained in MEK109.8g. After that, the temperature was raised to 80°C and the reaction was further carried out for 6 hours. Next, the reaction mixture was cooled to room temperature, and 83.3 g of MEK was added and diluted. The diluted solution was poured into a large amount of methanol to precipitate a polymer. Next, the polymer was collected by filtration, washed with methanol, and then vacuum-dried at 120°C for 16 hours. The yield of the polymer was 56.0 g, and the yield was 64%. In addition, in the polymer, the weight average molecular weight Mw was 4,500, and the dispersion degree (weight average molecular weight Mw/number average molecular weight Mn) was 1.59.

(Synthesis example 3: Synthesis of precursor polymer C) In a reaction vessel equipped with a reflux cooling tube and a dropping funnel, a 75% toluene solution of 2-norbornene (62.3g, 46.7g, 0.496mol converted to 2-norbornene), V-601 (4.6g, 0.020mol) ) And MEK 45.9g, stirred and dissolved. Next, after removing the dissolved oxygen in the system by bubbling with nitrogen, heating was performed, and when the internal temperature reached 60°C, maleic anhydride (48.7g, 0.496mol) was added and dissolved in MEK88.5g over 3 hours. In the solution. After that, the temperature was raised to 80°C and the reaction was further carried out for 6 hours. Next, the reaction mixture was cooled to room temperature, and 83.3 g of MEK was added and diluted. The diluted solution was poured into a large amount of methanol to precipitate a polymer. Next, the polymer was collected by filtration, washed with methanol, and then vacuum-dried at 120°C for 16 hours. The yield of the polymer was 92.5 g, and the yield was 93%. In addition, in the polymer, the weight average molecular weight Mw was 6,900, and the dispersion degree (weight average molecular weight Mw/number average molecular weight Mn) was 1.76.

(Synthesis example 4: Synthesis of precursor polymer D) In a reaction vessel equipped with a reflux cooling tube and a dropping funnel, a 75% toluene solution of 2-norbornene (NB) (179.7g, 134.8g, 1.43mol converted to 2-norbornene), V-601 (13.2g) , 0.057mol) and MEK101.0g, stir and dissolve. Next, the dissolved oxygen in the system was removed by bubbling with nitrogen, and then heated. When the internal temperature reached 60°C, N-cyclohexylmaleimide (25.7g, 0.14mol) was added over 3 hours. ) And maleic anhydride (126.4g, 1.29mol) dissolved in MEK304.0g. After that, the temperature was raised to 80°C and the reaction was further carried out for 6 hours. Next, the reaction mixture was cooled to room temperature, and 250 g of MEK was added and diluted. The diluted solution was poured into a large amount of methanol to precipitate a polymer. Next, the polymer was collected by filtration, washed with methanol, and then vacuum-dried at 120°C for 16 hours. The yield of the polymer was 250.0 g, and the yield was 83%. In addition, in the polymer, the weight average molecular weight Mw was 7,600, and the degree of dispersion (weight average molecular weight Mw/number average molecular weight Mn) was 1.88.

(Synthesis Example 5: Synthesis of precursor polymer E) In a reaction vessel equipped with a reflux cooling tube and a dropping funnel, a 75% toluene solution of 2-norbornene (NB) (18.8g, 14.1g, 0.15mol), MAN (14.7g, 0.15) mol), V-601 (1.4g, 6mmol), α-methylstyrene dimer (α-MSD, 1.4g, 6mmol) and MEK21.3g, stirred and dissolved. Next, after removing the dissolved oxygen in the system by bubbling with nitrogen, heating was performed, and the reaction was carried out at an internal temperature of 60°C for 16 hours. Next, the reaction mixture was cooled to room temperature, poured into a large amount of methanol, and a polymer was deposited. Next, the polymer was collected by filtration, washed with methanol, and then vacuum-dried at 120°C for 16 hours. The yield of the polymer was 6.7 g, and the yield was 23%. In addition, in the polymer, the weight average molecular weight Mw was 4,900, and the dispersion degree (weight average molecular weight Mw/number average molecular weight Mn) was 2.11. Table 1 shows the blending amounts of the components used in Synthesis Example 1 to Synthesis Example 5, and the weight average molecular weight and degree of dispersion of the obtained precursor polymer.

[Table 1] Precursor polymer Monomer 1 (norbornene) Monomer 2 (maleic anhydride) Monomer 3 (maleimide) Chain transfer agent Weight average molecular weight Mw Molecular weight distribution Mw/Mn species Parts by weight Mole% species Parts by weight Mole% species Parts by weight Mole% species Parts by weight Mole% Synthesis example 1 Precursor polymer A NB 73.6 50 MAN 76.7 50 - - - PEMP 15.3 2 3,500 1.62 Synthesis Example 2 Precursor polymer B NB 41.1 50 MAN 38.5 45 CMI 7.8 5 KBM-803 8.6 5 4,500 1.59 Synthesis Example 3 Precursor polymer C NB 46.7 50 MAN 48.7 50 - - - - - - 6,900 1.76 Synthesis Example 4 Precursor polymer D NB 134.8 50 MAN 126.4 45 CMI 25.7 5 - - - 7,600 1.88 Synthesis Example 5 Precursor polymer E NB 14.1 50 MAN 14.7 50 - - - α-MSD 1.4 2 4,900 2.11

(Synthesis Example 6: Synthesis of Polymer A-1) 20.0 g of the precursor polymer A synthesized in Synthesis Example 1 was dissolved in 30.0 g of MEK. Furthermore, 8.5 g of 2-hydroxyethyl methacrylate (HEMA) and 2.0 g of triethylamine (TEA) were added, and the temperature was increased to 70° C. and then reacted for 6 hours. Next, 4.4 g of glycidyl methacrylate (GMA) was added to the system, and the reaction was carried out at 70°C for a further 4 hours. The reaction mixture was cooled to room temperature and neutralized with formic acid. The solution was poured into a large amount of pure water, and the polymer was precipitated. The obtained polymer was collected by filtration, washed with pure water, and dissolved in PGMEA, and residual moisture was removed/concentrated under reduced pressure to obtain a polymer solution with a solid content of approximately 35%. The weight average molecular weight (Mw), molecular weight distribution, alkali dissolution rate, and double bond equivalent of the polymer thus obtained are shown in Table 2.

(Synthesis Example 7: Synthesis of Polymer B-1) 20.0 g of the precursor polymer B synthesized in Synthesis Example 2 was dissolved in 30.0 g of MEK. Furthermore, 11.6 g of 2-hydroxyethyl acrylate (HEA) and 2.0 g of triethylamine (TEA) were added, and the temperature was increased to 70°C, followed by a reaction for 6 hours. Next, the reaction mixture was cooled to room temperature and neutralized with formic acid. The solution was poured into a large amount of pure water, and the polymer was precipitated. The obtained polymer was collected by filtration, washed with pure water, and dissolved in PGMEA, and residual moisture was removed/concentrated under reduced pressure to obtain a polymer solution with a solid content of approximately 35%. The weight average molecular weight (Mw), molecular weight distribution, alkali dissolution rate, and double bond equivalent of the polymer thus obtained are shown in Table 2.

(Synthesis Example 8: Synthesis of Polymer C-1) 20.0 g of the precursor polymer C synthesized in Synthesis Example 3 was dissolved in 30.0 g of MEK. Furthermore, 8.5 g of 2-hydroxyethyl methacrylate (HEMA) and 2.0 g of triethylamine (TEA) were added, and the temperature was increased to 70° C. and then reacted for 6 hours. Next, 4.4 g of glycidyl methacrylate (GMA) was added to the system, and the reaction was carried out at 70°C for a further 4 hours. The reaction mixture was cooled to room temperature and neutralized with formic acid. The solution was poured into a large amount of pure water, and the polymer was precipitated. The obtained polymer was collected by filtration, washed with pure water, and dissolved in PGMEA, and residual moisture was removed/concentrated under reduced pressure to obtain a polymer solution with a solid content of approximately 35%. The weight average molecular weight (Mw), molecular weight distribution, alkali dissolution rate, and double bond equivalent of the polymer thus obtained are shown in Table 2.

(Synthesis Example 9: Synthesis of Polymer D-1) The precursor polymer D20.0 g synthesized in Synthesis Example 4 was dissolved in 30.0 g of MEK. Furthermore, 9.0 g of 2-hydroxyethyl acrylate (HEA) and 2.0 g of triethylamine (TEA) were added, and the temperature was increased to 70° C. and then reacted for 6 hours. Next, the reaction mixture was cooled to room temperature and neutralized with formic acid. The solution was poured into a large amount of pure water, and the polymer was precipitated. The obtained polymer was collected by filtration, washed with pure water, and dissolved in PGMEA, and residual moisture was removed/concentrated under reduced pressure to obtain a polymer solution with a solid content of approximately 35%. The weight average molecular weight (Mw), molecular weight distribution, alkali dissolution rate, and double bond equivalent of the polymer thus obtained are shown in Table 2.

(Synthesis Example 10: Synthesis of polymer E-1) The precursor polymer D5.0 g synthesized in Synthesis Example 5 was dissolved in 7.5 g of MEK. Furthermore, 2.9 g of 2-hydroxyethyl acrylate (HEA) and 0.5 g of triethylamine (TEA) were added, and the temperature was raised to 70°C, followed by a reaction for 6 hours. Next, the reaction mixture was cooled to room temperature and neutralized with formic acid. The solution was poured into a large amount of pure water, and the polymer was precipitated. The obtained polymer was collected by filtration, washed with pure water, and dissolved in PGMEA, and residual moisture was removed/concentrated under reduced pressure to obtain a polymer solution with a solid content of approximately 35%. The weight average molecular weight (Mw), molecular weight distribution, alkali dissolution rate, and double bond equivalent of the polymer thus obtained are shown in Table 2.

(Weight average molecular weight/molecular weight distribution) In addition, in this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw/Mn) are calculated based on the calibration curve of standard polystyrene (PS) obtained by GPC measurement. Styrene conversion value. The measurement conditions are as follows. Device: Gel Permeation Chromatography Device HLC-8320GPC manufactured by TOSOH CORPORATION Column: TSK-GEL Supermultipore HZ-M manufactured by TOSOH CORPORATION Detector: RI detector for liquid chromatography Measuring temperature: 40℃ Solvent: THF Sample concentration: 2.0mg/ml

(Double bond equivalent) The double bond equivalent of the polymer was measured by the following method. First, the measurement was performed by drying under reduced pressure to remove about 50 mg of the solvent from the polymer and about 5 mg of dimethyl terephthalate as the internal standard material, and dissolved in DMSO-d6. Regarding this solution, 1HNMR measurement was performed using a nuclear magnetic resonance spectroscopy apparatus JNM-AL300 (manufactured by JEOL Ltd.). Calculate the double bond per 1 mole from the integral ratio of the signal derived from the (meth)acrylic acid group (5-7ppm) of the obtained spectrum and the signal of the phenyl group (4H, 8.1ppm) of the internal standard material The polymer weight (g/mol, double bond equivalent).

[Table 2] polymer Precursor polymer Monomer 4 Weight average molecular weight Mw Molecular weight distribution Mw/Mn Alkali dissolution rate (Å/sec) Double bond equivalent (g/mol) species Parts by weight Mole% species Parts by weight Mole% Synthesis Example 6 Polymer A-1 A 20 100 HEMA GMA 8.5 4.4 62.5 30 4,200 1.54 3,000 600 Synthesis Example 7 Polymer B-1 B 20 100 HEA 11.6 50 7,600 1.80 20,500 710 Synthesis Example 8 Polymer C-1 C 20 100 HEMA GMA 8.5 4.4 62.5 30 7,800 1.70 12,800 540 Synthesis Example 9 Polymer D-1 D 20 100 HEA 9.0 50 8,600 1.89 12,300 620 Synthesis Example 10 Polymer E-1 E 5.0 100 HEA 2.9 50 4,800 2.41 2,900 720

<Preparation of photosensitive resin composition> With respect to 100 parts by mass of each of the polymers obtained in Synthesis Example 6 to Synthesis Example 10, 50 parts by mass of dineopentaerythritol hexaacrylate (crosslinking agent 1, DPHA) as a crosslinking agent was used as a photosensitizer Light free radical initiator (manufactured by BASF Corporation, Irgacure OXE01) 10 parts by mass, adhesion aid (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., KBM- 403) 1 part by mass and 0.1 part by mass of a surfactant (manufactured by DIC Corporation, F556) were dissolved in propylene glycol monomethyl ether acetate to prepare a solution with a solid content of 30%. After that, filtration was performed with a membrane filter having a pore diameter of 0.2 μm to prepare a photosensitive resin composition. Table 3 shows the blending amount of each component.

(Crosslinking agent) • Crosslinking agent 1: An acrylic crosslinking agent represented by the following formula (12) (DPHA manufactured by Daicel-Cytec Company, Ltd.).

[化43]

(Photosensitizer) • Photosensitizer 1: A photoradical polymerization initiator represented by the following formula (11) (Irgacure OXE02 manufactured by BASF Corporation) was used.

[化44]

(Adhesion aid) •Adhesion aid 1: 3-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.)

(Surfactant) Surfactant 1: Megaface F-556 (manufactured by DIC Corporation)

In addition, the obtained photosensitive resin composition was evaluated based on the following. (Light transmittance T _A ) Regarding each Example and each comparative example, the light transmittance of the resin film A formed using the photosensitive resin composition was measured in the following manner. First, after coating the obtained photosensitive resin composition on a glass substrate using a spin coater, it was baked on a hot plate at 110°C for 110 seconds. As the glass substrate, a 1737 glass substrate manufactured by Corning Incorporated Co., Ltd. having a size of 100 mm in length and 100 mm in width was used. After that, using a g+h+i-ray mask aligner (PLA-501F) manufactured by Canon Co., Ltd., g+h+i rays were exposed to the entire photosensitive resin composition ^{at 300 mJ/cm 2} . _{Next, the light transmittance T A} (%) of the resin film A with respect to light having a wavelength of 400 nm was measured. T _A light transmittance using an ultraviolet - visible spectrophotometer was measured. The results are shown in Table 3.

(Heat discoloration resistance T _B /T _A ×100) The resin film A obtained by the method described in the above-mentioned light transmittance T _A was heated at 250° C. for 1 hour in an atmospheric environment to obtain a resin film B. _{Thereafter, the light transmittance T B of} the resin film B with respect to light having a wavelength of 400 nm was evaluated. Let T _B /T _A ×100 be the thermal discoloration resistance %. The results are shown in Table 3.

[table 3] polymer Crosslinking agent Photosensitizer Adhesion aid Surfactant Transmittance T _{A before calcination Transmittance T B} after calcination at 250℃ Heat discoloration resistance T _B /T _A species Parts by weight species Parts by weight species Parts by weight species Parts by weight species Parts by weight Example 1 A-1 100 Crosslinking agent 1 DPHA 50 Photosensitizer 1 OXE01 5 Adhesive agent 1 KBM-403 1 Surfactant 1 F556 0.5 98.5% 95.9% 97.3% Example 2 B-1 100 98.5% 95.1% 96.5% Comparative example 1 C-1 100 98.2% 90.6% 92.3% Comparative example 2 D-1 100 98.5% 92.0% 93.5% Comparative example 3 E-1 100 98.3% 91.5% 93.1%

This application claims priority based on Japanese Application Japanese Patent Application No. 2019-088062 for which it applied on May 8, 2019, and uses all the contents of the disclosure here.

Claims (5)

A photosensitive resin composition comprising: a copolymer represented by the general formula (1); a crosslinking agent; and a photosensitizer,

In the general formula (1), l and m respectively represent the molar content of A and B in the copolymer, l+m=1, X is hydrogen or an organic group with 1 to 30 carbon atoms, and Y is -SR _5a , S is a sulfur atom, R _5a is an organic group with a carbon number of 1 or more and 30 or less, A includes the structural unit represented by the following formula (A1), and B includes the structural unit represented by the formula (B1) to (B6) At least one of

In the general formula (A1), R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or an organic group having from 1 to 30 carbon atoms or an organic group having an ethylenic double bond with carbon numbers of 1 to 30 or less. Base, n is 0, 1 or 2,

In the formula (B1), R ₅ is an organic group having a carbon number of 1 or more and 30 or less or an organic group having an ethylenic double bond having a carbon number of 1 or more and 30 or less,

In formula (B2), R ₆ and R ₇ are each independently an organic group having 1 to 30 carbon atoms or an organic group having an ethylenic double bond having 1 to 30 carbon atoms,

In the formula (B6), R ₈ is an organic group having a carbon number of 1 or more and 30 or less or an organic group having an ethylenic double bond having a carbon number of 1 or more and 30 or less. At least one of the structural unit represented by the formula (A1) and the structural unit represented by the formulas (B1) to (B6) contains an organic group having an ethylenic double bond and having a carbon number of 1 or more and 30 or less. The photosensitive resin composition of claim 1, wherein the photosensitive resin composition has a thermal discoloration resistance of 95% or more when measured under the following conditions, (condition) Regarding coating the photosensitive resin composition on a glass substrate on, carried out at 120 seconds 100 ℃ for sulfate and at an exposure amount of 300mJ / cm ² is obtained by exposing the resin film having a thickness of 3μm a, evaluated with a spectrophotometer wavelength of 400nm light transmittance , And set it as the transmittance T _A % before the heat resistance test; Regarding the resin film B obtained by heating the resin film A at 250°C for 1 hour in the atmosphere, the light transmittance of light with a wavelength of 400 nm was evaluated with a spectrophotometer, Let it be the transmittance T _B % after the heat resistance test; let T _B /T _A ×100 be the heat discoloration resistance %. The photosensitive resin composition of claim 1 or 2, wherein the weight average molecular weight of the copolymer is 1500 or more and 30,000 or less. A resin film composed of a cured product of the photosensitive resin composition according to any one of claims 1 to 3. An electronic device provided with the resin film of claim 4.