JP6661929B2 - Negative photosensitive resin composition, resin film and electronic device - Google Patents

Description

  The present invention relates to a polymer, a positive photosensitive resin composition, a negative photosensitive resin composition, a resin film, and an electronic device.

  As an insulating film constituting an electronic device, a resin film obtained by exposing a photosensitive resin composition may be used. As a technique relating to such a photosensitive resin composition, for example, a technique described in Patent Document 1 can be mentioned. Patent Document 1 discloses a radiation-sensitive resin composition containing a copolymer containing a polymerized unit of an unsaturated carboxylic acid and a polymerized unit of a specific compound, a 1,2-quinonediazide compound, and a latent acid generator. Has been described.

JP-A-9-230596

  However, in recent years, it has been required that the heat resistance required for a resin film constituting an electronic device be further increased, and a resin composition containing a polymer existing in the related art must sufficiently satisfy this requirement. Could not.

  In view of such circumstances, the present invention provides a polymer that improves the heat resistance of a resin film when a photosensitive resin composition is formed.

According to the present invention,
There is provided a negative photosensitive resin composition comprising a polymer containing a repeating unit represented by the following formulas (1), (2a) and (2b), and a photoradical generator .

（式（１）中、Ｒ_１、Ｒ_２、Ｒ_３およびＲ_４はそれぞれ独立して水素または炭素数１〜３０の有機基であり、Ｒ_１、Ｒ_２、Ｒ_３およびＲ_４のうち、少なくとも一つは、その構造中に環状エーテル基を備える。ｎは０、１または２である。）

(In the formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or an organic group having 1 to 30 carbon atoms, and among R ₁ , R ₂ , R ₃ and R ₄ , At least one has a cyclic ether group in its structure, where n is 0, 1 or 2.)

（式（２ｂ）中、Ｒ_５は炭素数１〜１８の有機基である。）

(In the formula (2b), R ₅ is an organic group having 1 to 18 carbon atoms.)

Further, according to the present invention, obtained by curing the resin compositions of the above SL, the resin film is provided.

  Further, according to the present invention, there is provided an electronic device including the above resin film.

The polymer of the present invention has a cyclic ether group in its structure, and as a result, has a dense connection structure when forming a resin film.
Accordingly, when the polymer of the present invention is applied to a use for forming a resin film (photosensitive resin composition or the like), the heat resistance of the resin film can be improved.

It is a sectional view showing an example of an electronic device concerning this embodiment. FIG. 2 is a cross-sectional view illustrating an example of a color filter according to the embodiment. 1 is a ¹ H-NMR chart of a polymer A1 used in Examples. 3 is a ¹ H-NMR chart of a polymer A2 used in Examples. 3 is a ¹ H-NMR chart of a polymer B1 used in Examples.

  Hereinafter, embodiments will be described with reference to the drawings as appropriate. In all the drawings, the same components are denoted by the same reference numerals, and description thereof will not be repeated. "-" Means the following from the above unless otherwise specified.

[polymer]
First, the polymer of the present embodiment will be described.
The polymer of the present embodiment contains the repeating units represented by the following formulas (1), (2a) and (2b).

（式（１）中、Ｒ_１、Ｒ_２、Ｒ_３およびＲ_４はそれぞれ独立して水素または炭素数１〜３０の有機基であり、Ｒ_１、Ｒ_２、Ｒ_３およびＲ_４のうち、少なくとも一つは、その構造中に環状エーテル基を備える。ｎは０、１または２である。）

(In the formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or an organic group having 1 to 30 carbon atoms, and among R ₁ , R ₂ , R ₃ and R ₄ , At least one has a cyclic ether group in its structure, where n is 0, 1 or 2.)

（式（２ｂ）中、Ｒ_５は炭素数１〜１８の有機基である。）

(In the formula (2b), R ₅ is an organic group having 1 to 18 carbon atoms.)

  Further, the polymer of the present embodiment may have structural units represented by the following formulas (2c) and (2d).

（Ｒ_６、Ｒ_７は、それぞれ独立して炭素数１〜１８の有機基である。）

(R ₆ and R ₇ are each independently an organic group having 1 to 18 carbon atoms.)

  In the polymer of the present embodiment, the total of the molar contents (mol%) of the structural units (2a) to (2d) (however, (2c) and (2d) may not be included) is m, and the structural unit (1 When the molar content (mol%) of (1) is 1, l + m = 1, and preferably 0.4 ≦ l ≦ 0.6 and 0.4 ≦ m ≦ 0.6.

The organic group having 1 to 30 carbon atoms constituting R ₁ , R ₂ , R ₃ and R ₄ may have at least one atom selected from O, N, S, P and Si in its structure. Good. Further, the organic groups constituting R ₁ , R ₂ , R ₃ and R ₄ may not have any acidic functional group. This makes it easy to control the acid value in the polymer.

In the present embodiment, examples of the organic group constituting R ₁ , R ₂ , R ₃ and R ₄ include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, and a cycloalkyl group. No.
Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, Octyl, nonyl, and decyl groups are included. Alkenyl groups include, for example, allyl, pentenyl, and vinyl. Examples of the alkynyl group include an ethynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkaryl group include a tolyl group and a xylyl group. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

Further, in the above-described alkyl group, alkenyl group, alkynyl group, alkylidene group, aryl group, aralkyl group, alkaryl group, and cycloalkyl group, one or more hydrogen atoms may be substituted with a halogen atom. Halogen atoms include fluorine, chlorine, bromine, and iodine.
Specific examples include a haloalkyl group in which one or more hydrogen atoms of an alkyl group are substituted with a halogen atom. When at least one of R ₁ , R ₂ , R ₃ and R ₄ is a haloalkyl group, when a cured film is formed using a polymer, the dielectric constant of the cured film can be reduced. Further, by using a haloalkyl alcohol group, not only the solubility in an alkali developer can be appropriately adjusted, but also the heat discoloration resistance can be improved.

In this embodiment, at least one of R ₁ , R ₂ , R ₃ and R ₄ has a cyclic ether group in its structure. More specifically, examples include a form containing a glycidyl group or an oxetanyl group in the structure.
Thereby, when a resin film is obtained from the polymer of the present embodiment, high heat resistance can be exhibited.

  Examples of such a group having a cyclic ether group in the structure include groups represented by the following formulas (20), (21), and (22).

In the formula (20), Y ₁ is a divalent organic group having 20 or less carbon atoms. By having such an organic group, it becomes possible to more effectively improve the heat resistance of a resin film formed using the photosensitive resin composition containing a polymer. The divalent organic group constituting Y ₁ is a linear or branched divalent hydrocarbon group which may have one or more of oxygen, nitrogen and silicon. In the present embodiment, Y ₁ can be, for example, a linear or branched alkylene group having 20 or less carbon atoms. From the viewpoint of improving the crack resistance, it is more preferable to employ a linear alkylene group as Y ₁ . One or more hydrogen atoms in the organic group constituting Y ₁ may be substituted by a halogen atom such as fluorine, chlorine, bromine or iodine.
Further, the carbon number of Y ₁ is preferably 1 or more and 18 or less, more preferably 1 or more and 15 or less, and further preferably 1 or more and 10 or less.

In the above formula (21), Y ₂ is a single bond or a divalent organic group having 1 to 10 carbon atoms. The divalent organic group constituting Y ₂ is a divalent hydrocarbon group which may have one or more of oxygen, nitrogen and silicon. In this embodiment, Y ₂ can be, for example, an alkylene group having 1 or 2 carbon atoms. One or more hydrogen atoms in the organic group constituting Y ₂ may be substituted by a halogen atom such as fluorine, chlorine, bromine or iodine.

Examples of the organic group having 1 to 30 carbon atoms having an oxetanyl group constituting R ₁ , R ₂ , R ₃ and R ₄ include an organic group represented by the following formula (22).

In the formula (22), X ₁ is a single bond or a divalent organic group having 1 to 7 carbon atoms, and X ₂ is hydrogen or an alkyl group having 1 to 7 carbon atoms. The divalent organic group constituting X ₁ is a linear or branched divalent hydrocarbon group which may have one or more of oxygen, nitrogen and silicon. Among them, an amino group (—NR—), an amide bond (—NHC (＝ O) —), an ester bond (—C (＝ O) —O—), a carbonyl group (—C (＝ O) —) or an ether Those having one or more linking groups such as a bond (-O-) in the main chain are more preferable, and those having one or more ester bonds, carbonyl groups or ether bonds in the main chain as the linking groups are particularly preferable. In addition, at least one hydrogen atom in the organic group constituting X ₁ may be substituted by a halogen atom such as fluorine, chlorine, bromine or iodine. The alkyl group constituting the _{X 2} is, for example, methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, tert- butyl group, a pentyl group, a neopentyl group, A hexyl group, and a heptyl group. Note that one or more hydrogen atoms contained in the alkyl group constituting X ₂ may be substituted with a halogen atom such as fluorine, chlorine, bromine, or iodine.
Examples of the organic group represented by the above formula (22) include those represented by the following formula (22a) and those represented by the following formula (22b).

As R ₅ in the formula (2b), an organic group having 1 to 18 carbon atoms is adopted. Here, examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, and a cycloalkyl group.
Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, Octyl, nonyl, and decyl groups are included. Alkenyl groups include, for example, allyl, pentenyl, and vinyl. Examples of the alkynyl group include an ethynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkaryl group include a tolyl group and a xylyl group. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
Further, this R ₅ may have a cyclic ether group in its structure, similarly to the aforementioned R ₁ , R ₂ , R ₃ and R ₄ .
Thereby, the heat resistance of the obtained resin film can be further improved.

When the polymer of this embodiment is used as a negative photosensitive resin composition, R ₅ preferably has a radical polymerizable group that initiates radical polymerization by a photo radical generator. More specifically, R ₅ preferably has a carbon-carbon double bond in its structure, and includes any group selected from the group consisting of a vinyl group, a vinylidene group, an acryloyl group, and a methacryloyl group. Is more preferable. Here, R ₅ is an aliphatic hydrocarbon group having 2 to 18 carbon atoms. In this case, for example, any one of the following formulas (I) and (II) can be employed as R ₅ .

（式（Ｉ）において、ｆは１〜５の整数であり、式（ＩＩ）においてｅは１〜９の整数である。）

(In the formula (I), f is an integer of 1 to 5, and in the formula (II), e is an integer of 1 to 9.)

Note that R ₅ is preferably the same in a plurality of repeating units represented by the formula (2b), but may be different for each repeating unit represented by the formula (2b).

Further, as R ₅ , an organic group having 8 to 18 carbon atoms including an aromatic ring may be used. In this case, for example, as the _{R 5,} vinyl aryl group _{(-Ar-CH = CH 2,} Ar represents an aromatic hydrocarbon group) can be employed.
It should be noted that R ₅ may not contain an acidic functional group.

The organic group having 1 to 18 carbon atoms constituting R ₆ and R ₇ in the formula (2c) may include one or more atoms of O, N, S, P, and Si in its structure. Further, the organic groups constituting R ₆ and R ₇ may not contain an acidic functional group. This makes it easy to control the acid value in the polymer.

In the present embodiment, examples of the organic group constituting R ₆ and R ₇ include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, and a cycloalkyl group. Here, examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, and heptyl. Groups, octyl, nonyl, and decyl groups. Alkenyl groups include, for example, allyl, pentenyl, and vinyl. Examples of the alkynyl group include an ethynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkaryl group include a tolyl group and a xylyl group. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
Further, R ₆ and R ₇ may have a cyclic ether group in the structure thereof, similarly to the aforementioned R ₁ , R ₂ , R ₃ and R ₄ .

  Further, in the above-described alkyl group, alkenyl group, alkynyl group, alkylidene group, aryl group, aralkyl group, alkaryl group, cycloalkyl group, and heterocyclic group, even when one or more hydrogen atoms are substituted with a halogen atom. Good. Halogen atoms include fluorine, chlorine, bromine, and iodine. Of these, a haloalkyl group in which one or more hydrogen atoms of an alkyl group are substituted with a halogen atom is preferable.

The polymer is, for example, an alternating copolymer in which repeating units derived from a norbornene-type monomer represented by the following formula (3) and maleic anhydride represented by the following formula (4) are alternately arranged. It is preferred that they are united. Note that the polymer may be a random copolymer or a block copolymer.
In addition, the repeating unit derived from maleic anhydride represented by the following formula (4) means the structural unit represented by the above formulas (2a) to (2d).

（式（３）中、ｎ、Ｒ_１、Ｒ_２、Ｒ_３およびＲ_４は式（１）で示したものと同義である。）

(In the formula (3), n, R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as those shown in the formula (1).)

In the molecular weight distribution curve obtained by, for example, GPC (Gel Permeation Chromatography), the polymer in the present embodiment preferably has a peak area at a molecular weight of 1,000 or less, 1% or less of the whole.
The present inventor has found that by reducing the amount of the low molecular weight component in the polymer, it is possible to suppress the deformation of the pattern of the film formed by the polymer during curing. For this reason, by setting the ratio of the peak area at a molecular weight of 1000 or less in the molecular weight distribution curve obtained by GPC to the above range, the pattern shape of the film made of the photosensitive resin composition containing the polymer can be improved. . The operation reliability of a liquid crystal display device and a solid-state imaging device having the film as a permanent film can be improved.
In addition, the lower limit of the amount of the low molecular weight component in the polymer is not particularly limited. However, the polymer in the present embodiment allows a case where the peak area at a molecular weight of 1000 or less is 0.01% or more of the whole in a molecular weight distribution curve obtained by GPC.
Further, the Mw (weight average molecular weight) of the polymer is, for example, 2500 or more and 35,000 or less, more preferably 3,000 or more and 32,000 or less, and further preferably 3500 or more and 30,000 or less.

The polymer in the present embodiment has, for example, Mw (weight average molecular weight) / Mn (number average molecular weight) of 1.5 or more and 2.5 or less. Note that Mw / Mn is a degree of dispersion that indicates the width of the molecular weight distribution.
The present inventor has found that by controlling the molecular weight distribution of the polymer to a certain range, it is possible to suppress the deformation of the pattern of the film formed by the polymer during curing. For this reason, by setting the Mw / Mn of the polymer to the above range, the pattern shape of the film made of the photosensitive resin composition containing the polymer can be improved. Such an effect is particularly remarkable when the low molecular weight component of the polymer is reduced as described above.

The weight average molecular weight (Mw), the number average molecular weight (Mn), and the degree of dispersion (Mw / Mn) indicating the width of the molecular weight distribution were determined from, for example, a calibration curve of standard polystyrene (PS) obtained by GPC measurement. Use polystyrene equivalents. The measurement conditions are, for example, as follows.
Tosoh Gel Permeation Chromatography System HLC-8320GPC
Column: Tosoh TSK-GEL Supermultipore HZ-M
Detector: RI detector for liquid chromatogram Measurement temperature: 40 ° C
Solvent: THF
Sample concentration: 2.0 mg / milliliter The amount of low molecular weight components in the polymer is the total area of components corresponding to a molecular weight of 1000 or less in the entire molecular weight distribution based on data on molecular weight obtained by, for example, GPC measurement. Is calculated from the ratio of

The polymer in the present embodiment contains, for example, an alkali metal. However, the concentration of the alkali metal in the polymer is, for example, 10 ppm or less (here, ppm means mass ppm).
By setting the concentration of the alkali metal in the polymer within the above range, the operation reliability of the liquid crystal display device and the solid-state imaging device including the permanent film can be improved. In addition, as long as it is within the above range, the alkali metal can be allowed to be contained in the polymer. That is, the step of opening the anhydride ring in the structural unit derived from maleic anhydride, which will be described later, can be performed by a treatment using an aqueous alkali solution. In this case, the process can be performed in a short time under mild conditions. In addition, control of the ring opening ratio in the polymer is easier than in the step of opening the anhydride ring using an acid catalyst.
The lower limit of the alkali metal concentration in the polymer is not particularly limited, but the present embodiment allows a case where the alkali metal concentration in the polymer is 0.01 ppm or more.

In this embodiment, the concentration of the alkali metal in the polymer is determined by measuring the alkali metal concentration with respect to the polymer solid content diluted with N-methylpyrrolidone, if necessary, using a flameless atomic absorption spectrophotometer. Obtained.
Further, examples of the alkali metal contained in the polymer according to the present embodiment include Na, K, and Li. These alkali metals are derived from, for example, an aqueous alkali solution in a ring-opening step (treatment S2) for opening a ring in a structural unit derived from maleic anhydride described later.

The alkali dissolution rate of the polymer in the present embodiment is, for example, not less than 500 ° / sec and not more than 30,000 ° / sec. The alkali dissolution rate of the polymer is determined, for example, by dissolving the polymer in propylene glycol monomethyl ether acetate, applying a polymer solution adjusted to a solid content of 20% by weight on a silicon wafer by a spin method, and soft-baking it at 110 ° C. for 100 seconds. The obtained polymer film is impregnated with a 2.38% aqueous solution of tetramethylammonium hydroxide at 23 ° C., and the time is visually measured until the polymer film disappears.
By setting the polymer dissolution rate in an alkali to 500 ° / sec or more, the throughput in the development step using an alkali developer can be improved. Further, by setting the rate of dissolving the alkali in the polymer to 30,000 ° / sec or less, the residual film ratio after the development step using an alkali developer can be improved. For this reason, it is possible to suppress the film loss due to the lithography process.
From the same viewpoint, the alkali dissolution rate of the polymer is more preferably 1000 ° / sec or more, and further preferably 2000 ° / sec or more. Further, the alkali dissolution rate of the polymer is more preferably 28000 / sec or less, and further preferably 25000 / sec or less.

(Method for producing polymer)
The polymer according to the present embodiment is manufactured, for example, as follows.

(Polymerization step (Process S1))
First, a norbornene-type monomer represented by the formula (3) and maleic anhydride as a monomer are prepared. In the norbornene-type monomer represented by the formula (3), n and R _{1 to} R ₄ can be the same as those in the formula (1).
The norbornene-type monomer represented by the formula (3) may be appropriately prepared according to a known method.

In this polymerization step, monomers other than the norbornene-type monomer represented by the formula (3) can be combined with a monomer having a norbornene skeleton as a main skeleton.
Examples of such a monomer include bicyclo [2.2.1] -hept-2-ene (common name: 2-norbornene), and further, as those having an alkyl group, 5-methyl-2-norbornene, Examples of those having an alkenyl group such as 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene and 5-decyl-2-norbornene include 5-allyl-2-norbornene, As those having an alkynyl group such as-(2-propenyl) -2-norbornene and 5- (1-methyl-4-pentenyl) -2-norbornene, those having an aralkyl group such as 5-ethynyl-2-norbornene Examples thereof include 5-benzyl-2-norbornene and 5-phenethyl-2-norbornene.
Other examples of the norbornene-type monomer include a functional group such as a crosslinkable group or a group containing a halogen atom such as fluorine in the structure of R ₁ , R ₂ , R ₃ , and R _{4 in} the formula (3). Can be employed.

Next, the norbornene-type monomer represented by the formula (3) is subjected to addition polymerization with maleic anhydride. Here, a copolymer (copolymer 1) of the norbornene-type monomer represented by the formula (3) and maleic anhydride is formed by radical polymerization.
The molar ratio of the norbornene-type monomer represented by the formula (3) to maleic anhydride (the number of moles of the compound represented by the formula (3): the number of moles of maleic anhydride) is 0.5: 1 to 1: 0. .5. Among them, from the viewpoint of controlling the molecular structure, it is preferable that the molar number of the norbornene-type monomer represented by the formula (3): the molar number of the maleic anhydride = 0.8: 1 to 1: 0.8.
In addition, at the time of this addition polymerization, a monomer that can be copolymerized other than the above-mentioned norbornene-type monomer and maleic anhydride may be added. Examples of such a monomer include a compound containing a group having an ethylenic double bond in the molecule. Here, specific examples of the group having an ethylenic double bond include an allyl group, an acryl group, a methacryl group, a maleimide group, and an aromatic vinyl group such as a styryl group and an indenyl group.

  As a polymerization method, for example, a method of performing polymerization using a radical polymerization initiator and, if necessary, a molecular weight modifier is preferable. In this case, methods such as suspension polymerization, solution polymerization, dispersion polymerization, and emulsion polymerization can be employed. Among them, solution polymerization is preferred. In the case of solution polymerization, all the monomers may be charged in a batch, or a part of the monomers may be charged in a reaction vessel, and the remainder may be dropped.

  For example, by dissolving a norbornene-type monomer represented by the formula (3), maleic anhydride, and a polymerization initiator in a solvent, and then heating for a predetermined time, the norbornene-type monomer represented by the formula (3): Solution polymerization with maleic anhydride. The heating temperature is, for example, 50 to 80 ° C., and the heating time is 10 to 20 hours.

  As the solvent used for the polymerization, for example, any one or more of tetrahydrofuran, toluene, methyl ethyl ketone, ethyl acetate and the like can be used.

As the radical polymerization initiator, any one or more of an azo compound and an organic peroxide can be used.
Examples of the azo compound include azobisisobutyronitrile (AIBN), dimethyl 2,2′-azobis (2-methylpropionate), and 1,1′-azobis (cyclohexanecarbonitrile) (ABCN). Any one or more of these can be used.
Examples of the organic peroxide include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP). , Any one or more of which can be used.

  The amount (molar number) of the radical polymerization initiator is preferably 1% to 10% of the total mole number of the norbornene-type monomer represented by the formula (3) and maleic anhydride. The weight-average molecular weight (Mw) of the obtained polymer can be adjusted to an appropriate range by appropriately setting the amount of the radical polymerization initiator within the above range and appropriately setting the reaction temperature and the reaction time.

By this polymerization step (treatment S1), copolymer 1 having a repeating unit represented by the following formula (5) and a repeating unit represented by the following formula (6) can be polymerized.
However, in the copolymer 1, R _{1 in} the structure of the formula (6) is preferably common to each repeating unit, but may be different for each repeating unit. The same applies to R _{2 to} R ₄ .

（式（６）中、ｎ、Ｒ_１、Ｒ_２、Ｒ_３およびＲ_４は式（１）で示したものと同義である。）

(In the formula (6), n, R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as those shown in the formula (1).)

  In the copolymer 1, the repeating unit represented by the formula (5) and the repeating unit represented by the formula (6) may be randomly arranged, or may be alternately arranged. There may be. Further, a block copolymer of a norbornene-type monomer represented by the formula (3) and maleic anhydride may be used. However, from the viewpoint of ensuring the uniformity of solubility of the photosensitive resin composition using the polymer produced in the present embodiment, the repeating unit represented by the formula (5) and the repeating unit represented by the formula (6) It is preferable that the structure is such that the units are alternately arranged. That is, it is preferable that the copolymer 1 has a repeating unit represented by the following formula (7).

（式（７）中、ｎ、Ｒ_１、Ｒ_２、Ｒ_３およびＲ_４は式（１）で示したものと同義である。また、ａは重合数を示す。）

(In the formula (7), n, R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as those shown in the formula (1), and a represents the number of polymerization.)

Here, R _{1 in} the structure of the formula (7) is preferably common to each repeating unit, but may be different for each repeating unit. The same applies to R _{2 to} R ₄ .

(Low molecular weight component removal step (processing S2))
Next, a polymer containing the copolymer 1 in addition to a large amount of a poor solvent, for example, hexane or methanol, is added to the organic layer containing the copolymer 1 and low molecular weight components such as residual monomers and oligomers. Is coagulated and precipitated. Here, the low molecular weight component includes residual monomers and oligomers, and further includes a polymerization initiator and the like. Next, filtration is performed, and the obtained coagulated product is dried. Thereby, a polymer containing the copolymer 1 from which the low molecular weight component has been removed as a main component (main product) can be obtained.

(Ring opening step (processing S3))
Next, among the repeating units having a cyclic structure derived from maleic anhydride in the obtained copolymer 1, the remaining repeating units are ring-opened while keeping some of the repeating units in a closed state. Thereby, the amount of the carboxyl group in the copolymer 1 can be adjusted.
In the present embodiment, it is preferable that, for example, 10% or more of the repeating units derived from maleic anhydride in the copolymer 1 are ring-opened. Among them, it is preferable to open 20% or more of the repeating units in the total number of repeating units having a cyclic structure derived from maleic anhydride in the copolymer 1. When the ring opening ratio is in the above range, it is easy to give the copolymer 1 a sufficient alkali developing solution.
As will be described later, in this ring opening step, a metal alkoxide as an (α) base, an (β) alcohol, an alkali metal salt, an alkali hydroxide or the like acts on a structural unit derived from maleic anhydride. It is done by that. That is, in this step, the structural unit derived from maleic anhydride is esterified with an alcohol (metal alkoxide) used simultaneously with ring opening.
Therefore, in this specification, this step is also referred to as “esterification step”. Further, the degree of esterification of the structural unit derived from maleic anhydride is referred to as “esterification ratio”.

Here, the esterification rate of the repeating unit derived from maleic anhydride can be calculated as follows using NMR.
Esterification ratio (%) = esterified carboxyl group (mol) / (acid anhydride group before esterification (mol)) × 100

In particular,
(Α) A metal alkoxide (β) alcohol as a base and one of an alkali metal salt and an alkali hydroxide are added to the reaction solution in which the copolymer 1 is polymerized in the polymerization step, and methyl ethyl ketone ( An organic solvent such as MEK) is further added, and the mixture is stirred at 50 to 100 ° C. for 10 to 20 hours to obtain a reaction liquid L1. In the reaction solution L1, some of the anhydride rings of the maleic anhydride-derived repeating unit of the copolymer 1 are opened, and some of the terminals formed by the ring opening are esterified. The remaining terminals are not esterified and have a metal salt structure.

In this embodiment, the mole number of the metal alkoxide, alkali metal salt or alkali hydroxide is preferably 50% or less of the mole number of maleic anhydride used in the polymerization step. Above all, the mole number of the metal alkoxide or alkali metal salt or alkali hydroxide is preferably 40% or less, more preferably 30% or less, of the mole number of maleic anhydride used in the polymerization step. preferable. By doing so, the amount of the metal alkoxide, alkali metal salt or alkali hydroxide can be reduced, and the alkali metal concentration in the finally obtained polymer can be reduced.
By reducing the concentration of the alkali metal in the polymer, migration of metal ions can be suppressed when a device using the polymer is formed.
In the present embodiment, the mole number of the metal alkoxide, alkali metal salt or alkali hydroxide can be 10% or more of the mole number of maleic anhydride used in the polymerization step.

As the above-mentioned metal alkoxide, those represented by M (OR ₅ ) (M is a monovalent metal, and R ₅ is an organic group having 1 to 18 carbon atoms) are preferable. Examples of the metal M include an alkali metal, and among them, sodium is preferable from the viewpoint of handleability. As R ₅ , those similar to R ₅ in formula (2b) can be mentioned.
Note that two or more different metal alkoxides may be used. However, from the viewpoint of production stability, it is preferable to use one kind of metal alkoxide.

On the other hand, as described above, the structure of copolymer 1 derived from maleic anhydride may be ring-opened in the presence of (β) alcohol and an alkali metal hydroxide as a base.
As the alkali metal salt or alkali hydroxide, sodium hydroxide or sodium acetate is preferable from the viewpoint of handleability.
As the alcohol, a monohydric alcohol (R ₅ OH) is preferable. R ₅ is an organic group may be used those described above.
Examples of the alcohol or the alcohol used as a raw material of the metal alkoxide include 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-octen-1-ol, 8-nonen-1-ol, 9-decene-1-ol, 10-undecene-1-ol, 2- Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 1,4-cyclohexane dimethanol monoacrylate, and 1,4-cyclohexane dimethanol monomethacrylate Over preparative and the like, can be used any one or more of these.

  The repeating unit derived from maleic anhydride opened in the ring opening step (treatment S3) has a structure represented by the following formula (8), and has a structure having a salt portion of a carboxyl group. Those having the structure of the formula (8) are referred to as copolymer 2. In the structure of the formula (8) and the structure of the formula (10) described later, a sodium ion is described as a corresponding metal ion. However, in view of the reactivity of the metal alkoxide, another metal ion is used. You can also.

（式（８）において、Ｒ_５は、前述したＲ_５と同様であり、前述したアルコールあるいは金属アルコキシド由来のものである。）

(In the formula (8), R ₅ is the same as the above-mentioned R ₅ and is derived from the above-mentioned alcohol or metal alkoxide.)

In the copolymer 2, a structure represented by the following formula (9) may be formed, albeit slightly. Even R ₅ in the formula (9) is the same as R ₅ mentioned above, is derived from an alcohol or a metal alkoxide mentioned above.

  In the copolymer 2, a structure represented by the following formula (10) may be formed, albeit slightly.

Next, an aqueous solution such as hydrochloric acid or formic acid is added to the reaction solution L1, and the copolymer 2 is treated with an acid to replace metal ions (Na ⁺ ) with protons (H ⁺ ). Thereby, in the copolymer 3 obtained by treating the copolymer 2 with an acid, the repeating unit derived from the ring-opened maleic anhydride represented by the formula (8) is represented by the following formula (11). Structure, and one end becomes a carboxyl group.

（式（１１）において、Ｒ_５は、前述したＲ_５と同様である。）

(In the formula (11), R ₅ is the same as R ₅ described above.)

  When the copolymer 2 has a structure represented by the formula (10), the structure has a structure represented by the following formula (12).

  The copolymer 3 obtained by treating the copolymer 2 with an acid has a repeating unit represented by the formula (6), a repeating unit represented by the formula (5), and a formula (11). It has a repeating unit and, in some cases, a structure of the formula (9) and a structure of the formula (12). And, of the total number of structural units derived from maleic anhydride, the repeating unit represented by the formula (5) is preferably at most 60%, more preferably at most 50%. When the repeating unit represented by the formula (5) and the repeating unit represented by the formula (11) (the structure of the formula (9) and the structure of the formula (12) are included), the repeating unit is represented by the formula (11). The ratio (molar ratio (formula (5): formula (11)) (structure of formula (9), formula (9)) of the repeating unit, the sum of the structure of formula (9) and the structure of formula (12) When the structure of 12) is included, the expression (11) + the expression (9) + the expression (12))) is, for example, 10: 1 to 1:10.

  Among them, a structure having the following formulas (13) and (14) as repeating units, and a structure derived from a norbornene-type monomer and a structure derived from a maleic anhydride monomer are preferably arranged alternately. .

In the formulas (13) and (14), n and R _{1 to} R ₄ have the same meanings as those shown in the formula (1). Further, in the structure of the formula (14), Z represents any one of —OH and —OR ₅ , and W represents a structure showing either one of them, and although both Z and W are slightly, includes a structure is -OR _5. R ₅ is the same as R ₅ described above.
In some cases, the repeating unit represented by the formula (14) may include a structure in which both Z and W are each —OH.

When formula (13) is a repeating unit, R ₁ is preferably common to each repeating unit, but may be different for each repeating unit. The same applies to R _{2 to} R ₄ .
Similarly, when Formula (14) is a repeating unit, R ₁ is preferably common to each repeating unit, but may be different for each repeating unit. The same applies to R _{2 to} R ₄ , W, and Z.

As described above, the ring opening step (processing S3) can be performed by adding a basic catalyst or an acid catalyst, but a step in which neither of these is added can be employed. In this case, the neutralization step and the water washing step accompanying the addition of the catalyst can be omitted. Incidentally, in a ring opening process according to the present embodiment (process S3), and without the addition of an acidic catalyst and a basic catalyst, the molar number of the added norbornene-type monomer in the polymerization step (process S1) a (mol) as M ₃ , 0.01 × M ₃ (mol) or more are not added. In the present embodiment, an embodiment in which an acidic catalyst and a basic catalyst are not added at all in the ring opening step (treatment S3) is also a preferred example.
The step of adding no catalyst can be achieved by adding a predetermined alcohol compound and then performing a heat treatment.

(Washing process (process S4))
Next, the solution containing the copolymer 3 obtained by the above steps is reprecipitated in water or washed with water to remove residual metal components and unreacted alcohol. In the case of reprecipitation, a polymer containing the copolymer 3 is dropped into a large amount of water to cause coagulation and precipitation. Next, filtration is performed, the obtained coagulated product is collected, and the washing operation with water is repeated several times. In the case of washing with water, washing is performed with a mixture of water and an organic solvent (for example, MEK (methyl ethyl ketone)), and then the aqueous layer is removed (first washing). Thereafter, a mixture of water and an organic solvent (for example, MEK (methyl ethyl ketone)) is added to the organic layer again, and the organic layer is washed (second washing). In the present embodiment, the above-described cleaning step (processing S4) is repeated, for example, five times or more, more preferably ten times. Thereby, the concentration of the alkali metal in the copolymer 3 can be sufficiently reduced. In the present embodiment, it is preferable to repeat the washing step (processing S4) so that the alkali metal concentration in the copolymer 3 becomes 10 ppm or less, preferably 5 ppm or less.

(Solvent replacement step (Process S5))
After the washing step (processing S4), solvent replacement can be performed. The solvent replacement can be performed, for example, by removing the compounds used in the treatments S1 to S4 by distillation under reduced pressure, and replacing the inside of the system while adding a product solvent such as PGMEA (propylene glycol monomethyl ether acetate). .

(Heating process (process S6))
In the present embodiment, by adjusting the ring-opening rate of the repeating unit derived from maleic anhydride in the above-described ring-opening step (treatment S3), an alkali developer of a polymer (for example, TMAH (aqueous tetramethylammonium hydroxide solution) Although the dissolution rate for ()) is adjusted, if it is necessary to further strictly adjust the dissolution rate, the main heating step (process S6) can be performed. In this heating step (processing S6), the dissolution rate of the polymer in the alkaline developer can be further adjusted by heating the copolymer 3.

  The heating step (processing S6) can be performed, for example, under the conditions of 100 ° C. or more and 140 ° C. or less, for 0.5 hour or more and 10 hours or less. Note that these heat treatment conditions can be appropriately adjusted according to a desired dissolution rate.

In this heating step (treatment S6), a part of the carboxyl group of the copolymer 3, that is, the carboxyl group formed at the terminal of the ring-opening structure of the structure derived from maleic anhydride is esterified. In addition, in the heating step (treatment S6), the ring-opened structure of the structure derived from maleic anhydride of the copolymer 3 is dehydrated and closed again.
Therefore, the copolymer 4 obtained through this step has a repeating unit represented by the formula (6), a repeating unit represented by the formula (5), a repeating unit represented by the formula (11), And a repeating unit represented by the formula (15).

In the formula (15), _{R 6} and _{R 7} are the same as _{R 6} and _{R 7} in the formula (2c), comprising a structure which is independent organic group having 1 to 18 carbon atoms.
In the structure represented by the formula (15), R ₇ is the aforementioned R ₅ , and the organic group having 1 to 18 carbon atoms of R ₆ is derived from the alcohol used in the main heating step (treatment S6). Including cases.
Further, the structure represented by the formula (15) may include the structure represented by the formula (9). In this case, R ₆ and R ₇ in the formula (15) are the same groups as R ₅ shown in the formula (9).
Further, the structure represented by the formula (15) may include a structure in which two carboxyl groups are esterified in the formula (12). In this case, R ₆ and R ₇ are both derived from the alcohol used in the main heating step (treatment S6).

Thereby, a product (polymer) having the copolymer 4 as a main product can be obtained.
Like the copolymer 3, the copolymer 4 preferably has a structure in which a structure derived from a norbornene-type monomer and a structure derived from a maleic anhydride monomer are alternately arranged. The copolymer 4 preferably has a structure represented by the formula (16) in addition to the formulas (13) and (14) described above.

In the formula (16), n, R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as those shown in the formula (1). X represents either one of -OR ₆ and -OR _7, Y represents any other. R ₆ and R ₇ are the same as in the above formula (15).

  Through the above steps, the polymer according to the present embodiment is obtained.

[Positive photosensitive resin composition]
Subsequently, the positive photosensitive resin composition according to the present embodiment will be described.
The positive photosensitive resin composition according to the present embodiment contains a photosensitive agent in addition to the above-described polymer.

  The photosensitive resin composition can include, for example, a photosensitive agent. As the photosensitive agent, for example, a diazoquinone-based photosensitive agent (diazoquinone compound) can be included. The diazoquinone-based photosensitive agent (diazoquinone compound) used as the photosensitive agent includes, for example, those exemplified below.

（ｎ２は、１以上５以下の整数である）

(N2 is an integer of 1 or more and 5 or less)

  In each of the above compounds, Q is any of the following structures (a), (b) and (c), or a hydrogen atom. However, at least one of Q included in each compound is any of the following structures (a), (b) and (c). From the viewpoints of transparency and dielectric constant of the obtained resin film, an o-naphthoquinonediazidosulfonic acid derivative in which Q is the structure (a) or the structure (b) is more preferable.

  The content of the photosensitizer in the positive photosensitive resin composition is preferably from 1 part by mass to 40 parts by mass, and more preferably from 5 parts by mass to 35 parts by mass with respect to 100 parts by mass of the whole polymer. Is more preferable. This makes it possible to effectively improve the balance of reactivity, stability over time, and developability of the positive photosensitive resin composition.

  The positive photosensitive resin composition can contain an acid generator that generates an acid by light or heat, for example. Examples of the photoacid generator that generates an acid by light include triphenylsulfonium trifluoromethanesulfonate, tris (4-t-butylphenyl) sulfonium-trifluoromethanesulfonate, and diphenyl [4- (phenylthio) phenyl] sulfonium trifluorotris Sulfonium salts such as pentafluoroethyl phosphate and diphenyl [4- (phenylthio) phenyl] sulfoniumtetrakis (pentafluorophenyl) borate; diazonium salts such as p-nitrophenyldiazonium hexafluorophosphate; ammonium salts; phosphonium salts; diphenyliodonium trifluoro Iodo such as methanesulfonate, (tricumyl) iodonium-tetrakis (pentafluorophenyl) borate Salts, quinonediazides, diazomethanes such as bis (phenylsulfonyl) diazomethane, sulfones such as 1-phenyl-1- (4-methylphenyl) sulfonyloxy-1-benzoylmethane, N-hydroxynaphthalimide-trifluoromethanesulfonate Acid esters, disulfones such as diphenyldisulfone, tris (2,4,6-trichloromethyl) -s-triazine, 2- (3,4-methylenedioxyphenyl) -4,6-bis- (trichloromethyl) It can have compounds such as triazines such as -s-triazine. The positive photosensitive resin composition according to the present embodiment can also include one or more photoacid generators exemplified above.

  Examples of the acid generator that generates an acid by heat (thermal acid generator) include SI-45L, SI-60L, SI-80L, SI-100L, SI-110L, and SI-150L (Sanshin Chemical Industry Co., Ltd.) ) Can be contained. The positive photosensitive resin composition in the present embodiment can also contain one or more of the thermal acid generators exemplified above. Further, in the present embodiment, it is also possible to use the photoacid generators exemplified above and these thermal acid generators in combination.

  When an acid generator is included in the positive photosensitive resin composition, the content is preferably 0.1 part by mass or more and 15 parts by mass or less based on 100 parts by mass of the whole polymer, and 0.5 part by mass. It is more preferable that the amount is not less than 10 parts by mass. This makes it possible to effectively improve the balance of reactivity, stability over time, and developability of the positive photosensitive resin composition.

The positive photosensitive resin composition of the present embodiment may contain a solvent. Examples of the solvent include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl carbinol (MIBC), gamma butyrolactone (GBL), N-methylpyrrolidone (NMP), methyl n -Amyl ketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, or a mixture thereof can be used. In addition, it is not limited to what was illustrated here.
The amount of the solvent to be added can be appropriately set according to the application to which the positive photosensitive resin composition is applied.

  Further, the positive photosensitive resin composition of the present embodiment may be a filler, a binder resin other than the above-mentioned polymer, a heat-resistant improver, a development aid, a plasticizer, a polymerization inhibitor, depending on the purpose and required characteristics of each application. , UV absorbers, antioxidants, matting agents, defoamers, leveling agents, antistatic agents, dispersants, slip agents, surface modifiers, thixotropic agents, thixotropic aids, silane and aluminum, Components other than the above essential components such as a coupling agent such as a titanium-based compound and a polyhydric phenol compound may be blended.

[Negative photosensitive resin composition]
Subsequently, the negative photosensitive resin composition according to the present embodiment will be described.
The negative photosensitive resin composition according to the present embodiment contains a photoradical generator in addition to the above-described polymer.

  Specific examples of the photoradical generator include, for example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl Propan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2- (Hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl ) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone and other alkylphenone compounds; benzophenone, 4,4'-bis (dimethylamino) benzophenone and 2-carboxybenzophenone compounds Benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4- Thioxanthone-based compounds such as diethylthioxanthone; 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis ( Chloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbokinylnaphthyl) -4,6-bis (trichloromethyl ) -Halomethylated triazine compounds such as -s-triazine; 2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 ' -Benzofuryl) vinyl] -1,3,4-oxadiazole, 4-oxadiazole, halomethylated oxadiazole-based compounds such as 2-trichloromethyl-5-furyl-1,3,4-oxadiazole; 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophene) Le) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5 ' -Biimidazole compounds such as -tetraphenyl-1,2'-biimidazole; 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone, 1- [9 Oxime ester compounds such as -ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); bis (η5-2,4-cyclopentadiene-1- Titanocene compounds such as yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium; benzoic acid esters such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid Compounds; acridine compounds such as 9-phenyl acridine; and the like.

  In the negative photosensitive resin composition of the present embodiment, the photo radical generator is preferably 5 parts by mass or more and 20 parts by mass or less, and more preferably 8 parts by mass or more and 15 parts by mass with respect to 100 parts by mass of the whole polymer. Parts or less.

  By using a photosensitizer or a photoradical polymerization accelerator together with the photoradical generator, the sensitivity and the degree of crosslinking can be further improved. For example, dye compounds such as xanthene dyes and coumarin dyes, dialkylaminobenzene compounds such as ethyl 4-dimethylaminobenzoate and 2-ethylhexyl 4-dimethylaminobenzoate, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole and the like And a mercapto hydrogen donor.

The negative photosensitive resin composition of the present embodiment may contain a solvent. Examples of the solvent include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl carbinol (MIBC), gamma butyrolactone (GBL), N-methylpyrrolidone (NMP), methyl n -Amyl ketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, or a mixture thereof can be used. In addition, it is not limited to what was illustrated here.
The amount of the solvent to be added can be appropriately set according to the application to which the negative photosensitive resin composition is applied.

  In addition, the negative photosensitive resin composition of the present embodiment may be a filler, a binder resin other than the polymer described above, an acid generator, a heat resistance improver, a development aid, a plasticizer, depending on the purpose and required characteristics of each application. , Polymerization inhibitors, ultraviolet absorbers, antioxidants, matting agents, defoaming agents, leveling agents, antistatic agents, dispersants, slip agents, surface modifiers, thixotropic agents, thixotropic agents, silanes A component other than the above-mentioned essential components such as a coupling agent such as aluminum, titanium, etc., and a polyhydric phenol compound may be blended.

[Colored photosensitive resin composition]
The positive photosensitive resin composition and the negative photosensitive resin composition of the present embodiment can be made into a colored photosensitive resin composition by including a coloring agent.
Such a colored photosensitive resin composition can be suitably used, for example, when producing a black matrix or a colored pattern constituting a color filter.

The colored photosensitive resin composition of the present embodiment contains a conventionally known pigment or dye.
As the pigment, an organic pigment or an inorganic pigment can be used.
As organic pigments, azo pigments, phthalocyanine pigments, polycyclic pigments (quinacridone, perylene, perinone, isoindolinone, isoindoline, dioxazine, thioindigo, anthraquinone, quinophthalone, metal complexes System, diketopyrrolopyrrole-based pigments), dye lake-based pigments and the like.
Inorganic pigments include white and extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.) and chromatic pigments (graphite, cadmium, chromium vermilion, nickel titanium, chromium titanium , Yellow iron oxide, red iron oxide, zinc chromate, lead red, ultramarine, navy blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), black pigment (carbon black, bone black, graphite, iron black, titanium black, etc.) And brilliant pigments (pearl pigments, aluminum pigments, bronze pigments, etc.) and fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.) can be used.

  Pigment colors that can be used include yellow, red, purple, blue, green, brown, black, and white.

  As the dye, for example, known dyes described in JP-A-2003-270428, JP-A-9-171108, JP-A-2008-50599, and the like can be used.

  The above colorants can be used alone or in combination of two or more. As the above-mentioned coloring agent, those having an appropriate average particle diameter can be used depending on the purpose and application. However, when transparency is required, particularly for a color filter coloring resist, the coloring agent is as small as 0.1 μm or less. The average particle diameter is preferable, and when a hiding property such as a paint is required, a large average particle diameter of 0.5 μm or more is preferable. In addition, the above-mentioned coloring materials have been subjected to surface treatment such as rosin treatment, surfactant treatment, resin-based dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, wax coating, etc., depending on the purpose and application. Is also good.

  The content ratio of the coloring agent in the colored photosensitive resin composition of the present embodiment may be appropriately set depending on the purpose and application, but from the viewpoint of balancing the coloring power and the dispersion stability, the colored photosensitive resin composition When the total solid content of the product (that is, the components excluding the solvent) is 100 parts by mass, it is preferably 3% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass or less, and further preferably 10% by mass or less. It is at least 50 mass%.

[Use]
The photosensitive resin composition (positive photosensitive resin composition, negative photosensitive resin composition) of the present embodiment can obtain a resin film obtained by forming a cured product.
In consideration of the high heat resistance, such a resin film can constitute a permanent film such as a protective film, an interlayer film, or a dam material. Thereby, it is possible to improve the durability and the like of the electronic device including the resin film as the permanent film.

In addition, since the photosensitive resin composition of this embodiment (positive photosensitive resin composition, negative photosensitive resin composition) uses a specific polymer, it has excellent heat resistance when obtaining a cured product. Give a cured product.
The 5% weight loss temperature of the cured product is preferably 335 ° C. or higher, more preferably 340 ° C. or higher.
The 5% weight loss temperature can be defined as a 5% weight loss temperature in the atmosphere using, for example, a thermobalance device (“TG-DTA2000” manufactured by Bruker AXS).

(Electronic equipment)
Next, an example of the electronic device 100 to which the photosensitive resin composition of the present embodiment is applied will be described.
The electronic device 100 shown in FIG. 1 is, for example, a semiconductor chip. In this case, for example, a semiconductor package is obtained by mounting electronic device 100 on a wiring board via bumps 52. The electronic device 100 includes a semiconductor substrate provided with a semiconductor element such as a transistor, and a multilayer wiring layer provided on the semiconductor substrate (not shown). In the uppermost layer of the multilayer wiring layers, an interlayer insulating film 30 and an uppermost layer wiring 34 provided on the interlayer insulating film 30 are provided. The uppermost layer wiring 34 is made of, for example, Al. Further, a passivation film 32 is provided on the interlayer insulating film 30 and the uppermost layer wiring 34. An opening through which the uppermost layer wiring 34 is exposed is provided in a part of the passivation film 32.

A redistribution layer 40 is provided on the passivation film 32. The rewiring layer 40 includes an insulating layer 42 provided on the passivation film 32, a rewiring 46 provided on the insulating layer 42, an insulating layer 44 provided on the insulating layer 42 and the rewiring 46, Having. In the insulating layer 42, an opening connected to the uppermost wiring 34 is formed. The rewiring 46 is formed on the insulating layer 42 and in an opening provided in the insulating layer 42, and is connected to the uppermost wiring 34. The insulating layer 44 has an opening connected to the rewiring 46.
In the present embodiment, at least one of the passivation film 32, the insulating layer 42, and the insulating layer 44 can be formed of, for example, a resin film formed by curing the above-described photosensitive resin composition. In this case, for example, the coating film formed of a photosensitive resin material is exposed to ultraviolet light, developed and patterned, and then heated and cured to form the passivation film 32, the insulating layer 42, or the insulating layer 44. It is formed.

  In an opening provided in the insulating layer 44, a bump 52 is formed via an UBM (Under Bump Metallurgy) layer 50, for example. The electronic device 100 is connected to a wiring board or the like via the bump 52, for example.

(Color filter)
Subsequently, an example of a color filter to which the colored photosensitive resin composition of the present embodiment is applied will be described with reference to FIG. Note that such a color filter can be provided in a liquid crystal display device or a solid-state imaging device.

  The color filter 20 shown in FIG. 2 includes a support 10 on which a black matrix 11 and a colored pattern 12 are formed. Further, a protective film 13 and a transparent electrode are formed on the black matrix 11 and the colored pattern 12. A layer 14 is provided.

The support 10 is generally made of a material that transmits light, and is made of, for example, a polymer of polyester, polycarbonate, polyolefin, polysulfone, cyclic olefin, and the like, in addition to glass.
Further, the support 10 may be subjected to corona discharge treatment, ozone treatment, chemical solution treatment, or the like, if necessary.
In this embodiment, the support 10 is preferably made of glass.

  The black matrix 11 is made of, for example, a cured product of the colored photosensitive resin composition when a black pigment or a black dye is used as the above-mentioned colorant.

  The coloring pattern 12 in the color filter 20 usually has three colors of red, green, and blue. The colored pattern 12 is constituted by a cured product of the colored photosensitive resin composition when a pigment or a dye corresponding to the color is used as the aforementioned colored photosensitive resin composition.

  The color filter 20 shown in FIG. The protective film 13 can be appropriately selected from known inorganic or organic materials used as a protective film for a color filter.

The color filter 20 shown in FIG. The transparent electrode layer 14 is made of indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO), or an alloy thereof.
As a specific forming method, a known method can be employed, and for example, a method such as a sputtering method, a vacuum evaporation method, and a CVD method can be employed.

  For such a color filter 20, the colored photosensitive resin composition according to the present embodiment can be applied when the black matrix 11 or the colored pattern 12 is formed, whereby the heat resistance as a resin film can be improved. it can.

（式（１）中、Ｒ _１ 、Ｒ _２ 、Ｒ _３ およびＲ _４ はそれぞれ独立して水素または炭素数１〜３０の有機基であり、Ｒ _１ 、Ｒ _２ 、Ｒ _３ およびＲ _４ のうち、少なくとも一つは、その構造中に環状エーテル基を備える。ｎは０、１または２である。）

（式（２ｂ）中、Ｒ _５ は炭素数１〜１８の有機基である。）
２．
１．に記載のポリマーであって、
重量平均分子量（Ｍｗ）が２５００以上３５０００以下である、ポリマー。
３．
１．または２．に記載のポリマーであって、アルカリ溶解速度が５００Å／秒以上３００００Å／秒以下である、ポリマー。
４．
１．ないし３．のいずれか一つに記載のポリマーと、
感光剤と、
を含む、ポジ型感光性樹脂組成物。
５．
４．に記載のポジ型感光性樹脂組成物であって、
前記感光剤は、ジアゾキノン系感光剤である、ポジ型感光性樹脂組成物。
６．
４．または５．に記載のポジ型感光性樹脂組成物であって、
硬化物の５％重量減少温度が３３５℃以上である、ポジ型感光性樹脂組成物。
７．
４．ないし６．のいずれか一つに記載のポジ型感光性樹脂組成物であって、
さらに着色剤を含む、ポジ型感光性樹脂組成物。
８．
１．ないし３．のいずれか一つに記載のポリマーと、
光ラジカル発生剤と、
を含む、ネガ型感光性樹脂組成物。
９．
８．に記載のネガ型感光性樹脂組成物であって、
前記式（２ｂ）中のＲ _５ は、その構造中に炭素−炭素二重結合を有する、ネガ型感光性樹脂組成物。
１０．
８．または９．に記載のネガ型感光性樹脂組成物であって、
前記式（２ｂ）中のＲ _５ は、その構造中に、ビニル基、ビニリデン基、アクリロイル基、メタクリロイル基からなる群より選ばれるいずれかの基を含む、ネガ型感光性樹脂組成物。
１１．
８．ないし１０．のいずれか一つに記載のネガ型感光性樹脂組成物であって、
硬化物の５％重量減少温度が３３５℃以上である、ネガ型感光性樹脂組成物。
１２．
８．ないし１１．のいずれか一つに記載のネガ型感光性樹脂組成物であって、
さらに着色剤を含む、ネガ型感光性樹脂組成物。
１３．
４．ないし７．のいずれか一つに記載のポジ型感光性樹脂組成物または８．ないし１２．のいずれか一つに記載のネガ型感光性樹脂組成物を硬化させてなる、樹脂膜。
１４．
１３．に記載の樹脂膜を備える電子装置。
It should be noted that the present invention is not limited to the above-described embodiment, but includes modifications and improvements as long as the object of the present invention can be achieved.
Hereinafter, examples of the reference embodiment will be additionally described.
1.
A polymer containing a repeating unit represented by the following formulas (1), (2a) and (2b).

(In the formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or an organic group having 1 to 30 carbon atoms, and among R ₁ , R ₂ , R ₃ and R ₄ , At least one has a cyclic ether group in its structure, where n is 0, 1 or 2.)

(In the formula (2b), R ₅ is an organic group having 1 to 18 carbon atoms.)
2.
1. The polymer according to the above,
A polymer having a weight average molecular weight (Mw) of 2,500 to 35,000.
3.
1. Or 2. 3. The polymer according to item 1, wherein the alkali dissolution rate is from 500 / sec to 30,000 / sec.
4.
1. Or 3. A polymer according to any one of the above,
A photosensitive agent,
A positive photosensitive resin composition comprising:
5.
4. The positive photosensitive resin composition according to the,
The positive photosensitive resin composition, wherein the photosensitive agent is a diazoquinone-based photosensitive agent.
6.
4. Or 5. The positive photosensitive resin composition according to the,
A positive photosensitive resin composition having a 5% weight loss temperature of a cured product of 335 ° C. or higher.
7.
4. Or 6. The positive photosensitive resin composition according to any one of the above,
A positive photosensitive resin composition further containing a colorant.
8.
1. Or 3. A polymer according to any one of the above,
A photoradical generator,
A negative photosensitive resin composition comprising:
9.
8. The negative photosensitive resin composition according to the,
R ₅ in the formula (2b) is a negative photosensitive resin composition having a carbon-carbon double bond in its structure.
10.
8. Or 9. The negative photosensitive resin composition according to the,
A negative photosensitive resin composition, wherein R ₅ in the formula (2b) contains, in its structure, any group selected from the group consisting of a vinyl group, a vinylidene group, an acryloyl group, and a methacryloyl group.
11.
8. Or 10. The negative photosensitive resin composition according to any one of the above,
A negative photosensitive resin composition wherein the 5% weight loss temperature of the cured product is 335 ° C. or higher.
12.
8. Or 11. The negative photosensitive resin composition according to any one of the above,
A negative photosensitive resin composition further containing a colorant.
13.
4. Or 7. 7. The positive photosensitive resin composition according to any one of the above, or Or 12. A resin film obtained by curing the negative photosensitive resin composition according to any one of the above.
14．
13. An electronic device comprising the resin film according to item 1.

Next, examples of the present invention will be described. In addition, Examples (Examples A1 to A4) relating to the positive photosensitive resin composition described later shall be replaced with Reference Examples.

[Example A]
First, each material used in Example A was prepared as described below.

(Polymer A1)
In a suitably sized reaction vessel equipped with a stirrer and a condenser, maleic anhydride (32.5 g, 0.33 mol), oxetane norbornene represented by the following formula (25) (78.5 g, 0.33 mol) and dimethyl 2,2'-Azobis (2-methylpropionate) (12.2 g, 0.05 mol) was weighed and dissolved in ethyl acetate. This dissolved solution was subjected to a heat treatment at 60 ° C. for 16 hours while stirring to remove dissolved oxygen in the system by nitrogen bubbling. Next, the solution cooled to room temperature was reprecipitated using a large amount of butanol, and the precipitate was collected by filtration. 20 g of butanol was mixed with the oxetane norbornene-maleic anhydride copolymer thus obtained and reacted at 115 ° C. for 16 hours. After the reaction, a large amount of propylene glycol monomethyl ether acetate (PGMEA) was added, and butanol was distilled off under reduced pressure. Butanol was completely removed from the system to obtain 110 g of a solution having a polymer solid content of 32%.

As described above, a polymer A1 having a structure represented by the following formula (30) was obtained. Note that m and n in the formula (30) and the formulas (31) and (32) described later are the degrees of polymerization of the respective structural units.
After sufficiently drying the obtained polymer A1, it was dissolved in d6-DMSO, and the ¹ H-NMR chart was measured. FIG. 3 shows the obtained chart.
Various properties of the obtained polymer are as shown below.
-Weight average molecular weight (Mw): 8,450
-Dispersion degree: 2.01
-Alkali dissolution rate: 4,300 A / sec

(Polymer A2)
In a reaction vessel of an appropriate size equipped with a stirrer and a cooling tube, maleic anhydride (32.5 g, 0.33 mol) and oxetane norbornene represented by the above formula (25) (78.5 g, 0.33 mol) are added. And dimethyl 2,2′-azobis (2-methylpropionate) (12.2 g, 0.05 mol) were weighed and dissolved in ethyl acetate. This dissolved solution was subjected to a heat treatment at 60 ° C. for 16 hours while stirring to remove dissolved oxygen in the system by nitrogen bubbling. Next, the solution dissolved at room temperature was reprecipitated using a large amount of methanol, and the precipitate was collected by filtration. It was sufficiently dried by a vacuum dryer to obtain an oxetane norbornene-maleic anhydride copolymer. 30 g of this polymer was dissolved in methyl ethyl ketone (MEK), 42 g of 3-ethyl-3-hydroxymethyloxetane and 1.5 g of sodium acetate were added, and reacted at 80 ° C. for 15 hours. After adding 6.0 g of formic acid to the solution after the reaction, the solution was reprecipitated using a large amount of pure water, and the precipitate was collected by filtration. It was dried in a vacuum drier to obtain 35 g of a polymer.

As described above, a polymer A2 having a structure represented by the following formula (31) was obtained.
The obtained polymer A2, was analyzed by ¹ H-NMR chart after having dissolved in d6-DMSO. FIG. 4 shows the obtained chart.
Various properties of the obtained polymer are as shown below.
-Weight average molecular weight (Mw): 6,770
-Degree of dispersion: 1.94
・ Alkali dissolution rate: 23,200 A / sec

(Polymer A3)
In a suitably sized reaction vessel equipped with a stirrer and a condenser, maleic anhydride (122.4 g, 1.25 mol), 2-norbornene (117.6 g, 1.25 mol) and dimethyl 2,2′-azobis ( 2-Methylpropionate) (11.5 g, 50.0 mmol) was weighed and dissolved in methyl ethyl ketone (150.8 g) and toluene (77.7 g). The solution was bubbled with nitrogen for 10 minutes to remove oxygen, and then heated at 60 ° C. for 16 hours with stirring. Thereafter, methyl ethyl ketone (320 g) was added to this solution, and then a suspension of sodium hydroxide (12.5 g, 0.31 mol), butanol (463.1 g, 6.25 mol), and toluene (480 g) was added. The mixture was added at 45 ° C. for 3 hours. Then, the mixture is cooled to 40 ° C., treated with formic acid (88 mass% aqueous solution, 49.0 g, 0.94 mol) to protonate, and then methyl ethyl ketone and water are added, and the aqueous layer is separated. , And inorganic residues were removed. Next, methanol and hexane were added, and the organic layer was separated to remove unreacted monomers. Further, propylene glycol monomethyl ether acetate (PGMEA) was added, and methanol and butanol in the system were distilled off under reduced pressure until the residual amount was less than 1%. As a result, 1107.7 g of a polymer solution having a solid content of 20% by mass was obtained (GPC Mw = 13,700, Mn = 7,030).

(Photosensitizer A1)
A photosensitive agent represented by the following formula (B-1) (product name: PA-28, manufactured by Daito Mix Corporation) was prepared.

  In addition, Q in the formula (B-1) is represented by a hydrogen atom or the above formula (B-2), and 90% of the whole Q is the above formula (B-2).

(Photoacid generator A1)
A cationic polymerization initiator SI-150 manufactured by Sanshin Chemical Industry Co., Ltd. was prepared.

(Crosslinking agent A1)
An epoxy compound represented by the following formula (VG3101 manufactured by PRINTECH CORPORATION) was prepared.

(Surfactant A1)
3-glycidoxypropyltrimethoxysilane (product name KBM-403 manufactured by Shin-Etsu Silicone Co., Ltd.) was prepared.

(Surfactant A2)
Fluorosurfactant Megafax F-556 (manufactured by DIC Corporation) was prepared.

[Preparation of positive photosensitive resin composition]
For each example and each comparative example, each raw material in the amount shown in Table 1 was prepared, dissolved in PGMEA (propylene glycol monomethyl ether acetate), and then filtered through a fluorine resin filter having a pore size of 0.2 μm. A positive photosensitive resin composition was obtained.
In preparing the positive photosensitive resin compositions of Examples and Comparative Examples, PGMEA (propylene glycol monomethyl ether acetate) was adjusted so that the polymer content was 25%.

(5% weight loss temperature)
The positive photosensitive resin composition obtained above was spin-coated (500 to 3000 rpm) on an aluminum substrate and baked on a hot plate at 100 ° C. for 120 seconds. Thereafter, the entire positive photosensitive resin composition was exposed to g + h + i rays at 300 mJ / cm ² , and then heated in an oven at 220 ° C. for 45 minutes. Thus, a resin film having a thickness of 2 μm without a pattern was obtained.
Using a thermobalance device (“TG-DTA2000” manufactured by Bruker AXS), the 5% weight loss temperature in the air was measured for the resin film. Table 1 shows the results.

[Example B]
First, each material used in Example B was prepared as described below.

(Polymer B1)
In a suitably sized reaction vessel equipped with a stirrer and a cooling tube, maleic anhydride (29.4 g, 0.3 mol) and oxetane norbornene represented by the above formula (25) (70.8 g, 0.3 mol) were added. And dimethyl 2,2′-azobis (2-methylpropionate) (6.9 g, 0.3 mol) were weighed and dissolved in methyl ethyl ketone. This dissolved solution was subjected to a heat treatment at 60 ° C. for 16 hours while stirring to remove dissolved oxygen in the system by nitrogen bubbling. Next, the above solution cooled to room temperature was reprecipitated using a large amount of methanol, and the precipitate was collected by filtration and dried with a vacuum drier to obtain 50 g of a white solid. 10 g of the oxetane norbornene-maleic anhydride copolymer thus obtained was mixed with 40 g of 4-hydroxybutyl acrylate, 0.5 g of sodium acetate and 0.5 g of hydroquinone, and reacted at 80 ° C. for 16 hours. After the reaction, the mixture was mixed with 25 g of acetone and 1.0 g of formic acid, and dropped into 750 g of pure water to reprecipitate and purify the polymer. After filtration through Nutsche, the mixture was dried with a vacuum drier to obtain 10.0 g of a white solid.

As described above, a polymer B1 having a structure represented by the following formula (32) was obtained.
The obtained polymer B1, was analyzed by ¹ H-NMR chart after having dissolved in d6-DMSO. FIG. 5 shows the obtained chart.
Various properties of the obtained polymer are as shown below.
-Weight average molecular weight (Mw): 8,800
-Degree of dispersion: 1.73
-Alkali dissolution rate: 23,300 A / sec
Esterification rate (quantified by NMR; “n / (m + n)” in the formula): 70%

(Polymer B2)
In a suitably sized reaction vessel equipped with a stirrer and a condenser, maleic anhydride (735 g, 7.5 mol), 2-norbornene (706 g, 7.5 mol) and dimethyl 2,2′-azobis (2-methylpro (Pionate) (69 g, 0.3 mol) was weighed and dissolved in methyl ethyl ketone and toluene. This dissolved solution was subjected to a heat treatment at 60 ° C. for 15 hours while stirring, after removing dissolved oxygen in the system by nitrogen bubbling. Thus, a copolymer of 2-norbornene and maleic anhydride was obtained. 10 g of the 2-norbornene-maleic anhydride copolymer thus obtained was mixed with 50 g of hydroxyethyl methacrylate and 0.5 g of hydroquinone, and reacted at 100 ° C. for 16 hours. After the reaction, the mixture was mixed with 25 g of acetone, and then dropped into 750 g of pure water to reprecipitate and purify the polymer. After filtration through Nutsche, the mixture was dried with a vacuum drier to obtain 9.8 g of a white solid. The molecular weight was 12,200, the degree of dispersion was 1.89, and the alkali dissolution rate was 21,240 ° / sec.

(Photoradical generator B1)
A compound represented by the following formula (Irgacure OXE02 manufactured by BASF) was prepared.

(Surfactant B1)
3-glycidoxypropyltrimethoxysilane (product name KBM-403 manufactured by Shin-Etsu Silicone Co., Ltd.) was prepared.

(Surfactant B2)
Fluorosurfactant Megafax F-556 (manufactured by DIC Corporation) was prepared.

[Preparation of negative photosensitive resin composition]
In Examples and Comparative Examples, each raw material in the amount shown in Table 2 was prepared, dissolved in PGMEA (propylene glycol monomethyl ether acetate), and then filtered through a fluororesin filter having a pore diameter of 0.2 μm to obtain a negative mold. A photosensitive resin composition was obtained.
In preparing the negative photosensitive resin compositions of Examples and Comparative Examples, PGMEA (propylene glycol monomethyl ether acetate) was adjusted to have a polymer content of 25%.

(5% weight loss temperature)
The negative photosensitive resin composition obtained above was spin-coated (500 to 3000 rpm) on an aluminum substrate and baked on a hot plate at 100 ° C. for 120 seconds. Thereafter, the entire negative photosensitive resin composition was exposed to g + h + i rays at 300 mJ / cm ² , and then heated in an oven at 220 ° C. for 45 minutes. Thus, a resin film having a thickness of 2 μm without a pattern was obtained.
Using a thermobalance device (“TG-DTA2000” manufactured by Bruker AXS), the 5% weight loss temperature in the air was measured for the resin film. Table 2 shows the results.

  As is clear from the results in Tables 1 and 2, the value of the 5% weight loss temperature of the resin film was improved by providing a specific cross-linking site in the polymer structure.

The polymer of the present invention can improve, for example, heat resistance as a resin film obtained when applied as a photosensitive resin composition.
In addition, even for uses other than the photosensitive resin composition, it can be expected to be appropriately applied to uses requiring heat resistance.

DESCRIPTION OF SYMBOLS 10 Support 11 Black matrix 12 Coloring pattern 13 Protective film 14 Transparent electrode layer 20 Color filter 30 Interlayer insulating film 32 Passivation film 34 Top layer wiring 40 Rewiring layers 42 and 44 Insulating layer 46 Rewiring 50 UBM layer 52 Bump 100 Electronic device

Claims (9)

A negative photosensitive resin composition comprising a polymer containing repeating units represented by the following formulas (1), (2a) and (2b), and a photoradical generator.

(In the formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or an organic group having 1 to 30 carbon atoms, and among R ₁ , R ₂ , R ₃ and R ₄ , At least one has a cyclic ether group in its structure, where n is 0, 1 or 2.)

(In the formula (2b), R ₅ is an organic group having 1 to 18 carbon atoms.) A negative photosensitive resin composition according to claim 1,
A negative photosensitive resin composition wherein the polymer has a weight average molecular weight (Mw) of 2,500 to 35,000. The negative photosensitive resin composition according to claim 1 or 2 ,
A negative photosensitive resin composition wherein the alkali dissolution rate of the polymer is from 500 / sec to 30000 / sec. The negative photosensitive resin composition according to any one of claims 1 to 3 , wherein
R ₅ in the formula (2b) is a negative photosensitive resin composition having a carbon-carbon double bond in its structure. A negative photosensitive resin composition according to any one of claims 1 to 4 , wherein
A negative photosensitive resin composition, wherein R ₅ in the formula (2b) contains, in its structure, any group selected from the group consisting of a vinyl group, a vinylidene group, an acryloyl group, and a methacryloyl group. It is a negative photosensitive resin composition according to any one of claims 1 to 5 ,
A negative photosensitive resin composition having a cured product having a 5% weight loss temperature of 335 ° C or more. A negative photosensitive resin composition according to any one of claims 1 to 6 , wherein
A negative photosensitive resin composition further containing a colorant. A resin film obtained by curing the negative photosensitive resin composition according to any one of claims 1 to 7 . An electronic device comprising the resin film according to claim 8 .

Images