JPWO2015141525A1 - Photosensitive resin composition and electronic device - Google Patents

Abstract

The photosensitive resin composition is a photosensitive resin composition used for forming a permanent film, includes a polymer having a cyclic olefin structural unit, and has a PED of 10% or less measured under specific conditions (A). And the swelling ratio measured under the specific condition (B) is 20% or less.

Description

  The present invention relates to a photosensitive resin composition 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 regarding such a photosensitive resin composition, for example, the one 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. Have been described.

Japanese Patent Laid-Open No. 9-230596

  Further improvement in manufacturing stability is required for an electronic device including a permanent film formed using a photosensitive resin composition.

According to the present invention,
A photosensitive resin composition used to form a permanent film,
Including a polymer having a cyclic olefin structural unit;
PED (Post Exposure Delay) measured under the following condition (A) is 10% or less,
A photosensitive resin composition having a swelling ratio of 20% or less measured under the following condition (B) is provided.

<Condition (A)>
A resin film obtained by pre-baking the photosensitive resin composition at 100 ° C. for 120 seconds is exposed by irradiating g + h + i rays using a mask having a mask pattern with a width of 5 μm. Next, the resin film is developed by immersing it in a 0.5 mass% tetramethylammonium hydroxide aqueous solution maintained at a liquid temperature of 23 ± 1 ° C. for 90 seconds. At this time, the width of the pattern corresponding to the mask pattern of the sample developed immediately after exposure was set to W ₁ (= 5 μm), and the temperature was maintained at 23 ± 1 ° C. and humidity 40 ± 5% for 6 hours after exposure. The width of the pattern corresponding to the mask pattern of the sample developed after being placed in the room is W ₂ , and (W ₁ −W ₂ ) / W ₁ × 100 (%) is PED.

<Condition (B)>
The resin film obtained by pre-baking the photosensitive resin composition at 100 ° C. for 120 seconds was developed with a 0.5 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 90 seconds, Rinse with water. Next, the entire surface of the resin film is exposed with g + h + i line at 300 mJ / cm ² , and then heat treatment is performed at 230 ° C. for 60 minutes. Next, the resin film is immersed in a mixed solution of monoethanolamine and dimethyl sulfoxide (= 7: 3) at 70 ° C. for 15 minutes. At this time, the film thickness of the resin film after the heat treatment is a first film thickness, and the film thickness after immersion in the mixed solution is a second film thickness.
[(Second film thickness−first film thickness) / (first film thickness)] × 100 (%) is defined as a swelling ratio.

Moreover, according to the present invention,
An electronic device provided with the cured film of the above-mentioned photosensitive resin composition is provided.

  According to the present invention, the manufacturing stability of an electronic device can be improved.

  The above-described object and other objects, features, and advantages will become more apparent from the preferred embodiments described below and the accompanying drawings.

It is sectional drawing which shows an example of an electronic device.

  Hereinafter, embodiments will be described with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate.

  The photosensitive resin composition which concerns on this embodiment is a photosensitive resin composition used in order to form a permanent film | membrane, Comprising: The polymer which has a cyclic olefin structural unit is included. Moreover, the PED measured by the following conditions (A) is 10% or less, and the swelling rate measured by the following conditions (B) is 20% or less.

<Condition (A)>
A resin film obtained by pre-baking the photosensitive resin composition at 100 ° C. for 120 seconds is exposed by irradiating g + h + i rays using a mask having a mask pattern with a width of 5 μm. Next, the resin film is developed by immersing it in a 0.5 mass% tetramethylammonium hydroxide aqueous solution maintained at a liquid temperature of 23 ± 1 ° C. for 90 seconds. At this time, the width of the pattern corresponding to the mask pattern of the sample developed immediately after exposure was set to W ₁ (= 5 μm), and the temperature was maintained at 23 ± 1 ° C. and humidity 40 ± 5% for 6 hours after exposure. The width of the pattern corresponding to the mask pattern of the sample developed after being placed in the room is W ₂ , and (W ₁ −W ₂ ) / W ₁ × 100 (%) is PED.

<Condition (B)>
The resin film obtained by pre-baking the photosensitive resin composition at 100 ° C. for 120 seconds was developed with a 0.5 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 90 seconds, and then purified water. Rinse with. Next, the entire surface of the resin film is exposed at 300 mJ / cm ² with g + h + i line, and then heat treatment is performed at 230 ° C. for 60 minutes. Next, the resin film is immersed in a mixed solution of monoethanolamine and dimethyl sulfoxide (= 7: 3) at 70 ° C. for 15 minutes. At this time, the film thickness of the resin film after the heat treatment is defined as a first film thickness, and the film thickness after immersion in the mixed liquid is defined as a second film thickness.
[(Second film thickness−first film thickness) / (first film thickness)] × 100 (%) is defined as a swelling ratio.

One index for evaluating the manufacturing stability of an electronic device including a permanent film formed using a photosensitive resin composition is, for example, dimensional accuracy in a lithography process for patterning the permanent film. However, in the lithography process, there is a concern that pattern dimensions may be shifted due to slight changes in process conditions and environment. Such a shift can be particularly noticeable with the recent miniaturization of patterns. For this reason, it is required to stably realize higher dimensional accuracy of patterning.
The present inventor simultaneously controls the PED measured under the condition (A) and the swelling ratio measured under the condition (B), so that the process margin and chemical resistance of the photosensitive resin composition can be reduced. It has been found that it is possible to improve the balance and contribute to the realization of more sophisticated and stable patterning dimensional accuracy. The process margin refers to an allowable range with respect to variations in process parameters in the entire permanent film manufacturing process, including a development margin in a lithography process. Moreover, chemical | medical solution tolerance refers to the tolerance with respect to the various chemical | medical solution which can be used in the production process of a permanent film. In the present embodiment, based on such knowledge, the PED measured by the condition (A) is 10% or less, and the swelling ratio measured by the condition (B) is 20% or less. A resin composition is provided. Therefore, according to this embodiment, it is possible to realize a photosensitive resin composition that can improve the manufacturing stability of an electronic device.

  Hereinafter, the photosensitive resin composition according to the present embodiment and the electronic device 100 including a permanent film formed using the photosensitive resin composition will be described in detail.

First, the photosensitive resin composition according to this embodiment will be described.
The photosensitive resin composition is used for forming a permanent film. The permanent film is composed of a cured film obtained by curing the photosensitive resin composition. In this embodiment, for example, after a coating film composed of a photosensitive resin composition is patterned into a desired shape by exposure and development, a permanent film is formed by curing the coating film by heat treatment or the like.

Examples of the permanent film formed using the photosensitive resin composition include an interlayer film, a surface protective film, and a dam material. The application of the permanent film is not limited to these.
The interlayer film refers to an insulating film provided in a multilayer structure, and the kind thereof is not particularly limited. Examples of the interlayer film include those used in semiconductor device applications such as an interlayer insulating film constituting a multilayer wiring structure of a semiconductor element, a buildup layer or a core layer constituting a circuit board. Further, as the interlayer film, for example, a flattening film that covers a thin film transistor (TFT) in the display device, a liquid crystal alignment film, and a protrusion provided on a color filter substrate of an MVA (Multi Domain Vertical Alignment) type liquid crystal display device Or what is used in display apparatus uses, such as a partition for forming the cathode of an organic EL element, is also mentioned.
The surface protective film refers to an insulating film that is formed on the surface of an electronic component or an electronic device and protects the surface, and the type thereof is not particularly limited. Examples of such a surface protective film include a passivation film or a buffer coat layer provided on a semiconductor element, or a cover coat provided on a flexible substrate. The dam material is a spacer used to form a hollow portion for arranging an optical element or the like on the substrate.

  As described above, the photosensitive resin composition has a PED measured by the above condition (A) of 10% or less. Thereby, it can contribute to the improvement of the balance of the process margin and chemical | medical solution tolerance of the photosensitive resin composition. In addition, since it is easy to form a pattern with high accuracy, it is possible to improve the reliability of the electronic device. In addition, the lower limit value of PED measured by the above condition (A) is not particularly limited, but may be 0.1%, for example.

  Moreover, as for the photosensitive resin composition, the swelling rate measured by the said conditions (B) is 20% or less as mentioned above. Thereby, it can contribute to the improvement of the balance of the process margin and chemical | medical solution tolerance of the photosensitive resin composition. In addition, from the viewpoint of improving the chemical resistance more effectively, the swelling rate measured by the above condition (B) is more preferably 15% or less, and particularly preferably 10% or less. In addition, the lower limit value of the swelling rate measured under the above condition (B) is not particularly limited, but can be set to 0.1%, for example.

The PED measured under the above condition (A) measures the variation of the pattern width due to holding after exposure. As one of the factors that cause the variation in the pattern width, for example, the progress of the curing reaction in the photosensitive resin composition is assumed. On the other hand, the swelling rate measured under the above condition (B) measures the rate of change of the film thickness by dipping in a mixed solution of monoethanolamine and dimethyl sulfoxide. It is considered that this change in film thickness can be suppressed, for example, by improving the degree of curing of the photosensitive resin composition. Therefore, the PED measured under the condition (A) and the swelling rate measured under the condition (B) are mutually contradictory factors, and it is difficult to reduce both of them.
The present inventor measures PED measured by the above condition (A) and the above condition (B) by highly controlling the types and blending amounts of the respective components contained in the photosensitive resin composition. It came to obtain the photosensitive resin composition whose swelling rate is in the desired numerical range. Thus, as a result of intensive studies by the present inventors, it has become possible to realize a photosensitive resin composition having an excellent balance between process margin and chemical resistance. Thereby, the dimensional accuracy of patterning can be improved and it can contribute to the improvement of the manufacturing stability of an electronic device.

  The photosensitive resin composition preferably has a recover rate of 97% or more and 103% or less measured under the following condition (C), for example. Thereby, it becomes possible to improve the chemical | medical solution tolerance of the photosensitive resin composition more effectively. Moreover, the dimensional accuracy of the pattern obtained using the photosensitive resin composition can be made higher.

<Condition (C)>
The resin film obtained by pre-baking the photosensitive resin composition at 100 ° C. for 120 seconds was developed with a 0.5 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 90 seconds, and then purified water. Rinse with. Next, the entire surface of the resin film is exposed with g + h + i line at 300 mJ / cm ² , and then a first heat treatment is performed at 230 ° C. for 60 minutes. Next, the resin film is immersed in a mixed solution of monoethanolamine and dimethyl sulfoxide (= 7: 3) at 70 ° C. for 15 minutes. Next, a second heat treatment is performed on the resin film at 230 ° C. for 15 minutes. At this time, the film thickness after the first heat treatment of the resin film is the first film thickness, and the film thickness after the second heat treatment is the third film thickness.
[(Third film thickness) / (first film thickness)] × 100 (%) is defined as a recovery rate.

  From the viewpoint of improving the chemical resistance of the photosensitive resin composition, the recovery rate measured by the above condition (C) is more preferably 97% or more and 102% or less. In the present embodiment, for example, the recovery rate measured under the above condition (C) can be controlled by appropriately controlling the type and blending amount of each component contained in the photosensitive resin composition.

  The photosensitive resin composition includes a polymer (a) having a cyclic olefin structural unit. Thereby, it becomes possible to improve the balance of various properties required for the permanent film, such as process margin, chemical resistance, rework characteristics, and transparency.

(Polymer (a))
The polymer (a) is a homopolymer or a copolymer having a cyclic olefin structural unit. Examples of the cyclic olefin monomer forming the cyclic olefin structural unit include monocyclic compounds such as cyclohexene and cyclooctene, norbornene, norbornadiene, dicyclopentadiene, dihydrodicyclopentadiene, tetracyclododecene, tricyclopentadiene, dihydrotricyclopentadiene. , Tetracyclopentadiene, and polycyclic compounds such as dihydrotetracyclopentadiene. These cyclic olefin monomers may be substituted with one or more functional groups. The polymer (a) can be formed using one or two or more of these monomers.

  In the present embodiment, examples of the polymer (a) include those containing a structural unit represented by the following formula (1). Thereby, the balance of process margin, chemical solution resistance, rework characteristics, transparency, etc. can be improved more effectively.

In the above formula (1), n is 0, 1 or 2. R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or an organic group having 1 to 10 carbon atoms. When the polymer (a) includes a plurality of structural units represented by the above formula (1), the structure of each structural unit represented by the above formula (1) can be determined independently.

Examples of the organic group having 1 to 10 carbon atoms 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. Groups. The organic group may be a carboxyl group or an organic group having a hetero ring such as an epoxy ring or an oxetane ring.
As the alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, An octyl group, a nonyl group, and a decyl group are mentioned. Examples of the alkenyl group include allyl group, pentenyl group, and vinyl group. An ethynyl group is mentioned as an alkynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a phenyl group and a naphthyl 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. In the organic group constituting R ₁ , R ₂ , R ₃ and R ₄ , one or more hydrogen atoms may be substituted with a halogen atom such as fluorine, chlorine, bromine or iodine.

From the viewpoint of effectively improving the temporal stability of the photosensitive resin composition, a structural unit in which at least one of R ₁ , R ₂ , R ₃ and R ₄ is an organic group having an oxetane ring or an epoxy ring is used. It is preferable to include in polymer (a). In this case, the polymer (a) contains at least one of an oxetane group or an epoxy group. Further, from the viewpoint of further improving the temporal stability and chemical resistance, any one of R ₁ , R ₂ , R ₃ and R ₄ is an organic group having an oxetane ring or an epoxy ring, and the other is hydrogen. Particular preference is given to including certain structural units in the polymer (a).

Examples of the organic group having an oxetane ring constituting R ₁ , R ₂ , R ₃ and R ₄ include those represented by the following formula (2).

Wherein (2), X ₁ is a single bond or a divalent organic group having 1 to 6 carbon atoms, X ₂ is hydrogen or an alkyl group of 1 to 7 carbon atoms. The divalent organic group constituting X ₁ is a linear or branched divalent hydrocarbon group which may have any one kind or two or more kinds of oxygen, nitrogen and silicon. Among these, 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 at least one linking group such as a bond (—O—) in the main chain are more preferable, and those having at least one carbonyl group or ether bond in the main chain as a linking group are particularly preferable. One or more hydrogen atoms in the organic group constituting X ₁ may be substituted with a halogen atom such as fluorine, chlorine, bromine or iodine. The alkyl group constituting X ₂ is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, A hexyl group and a heptyl group are mentioned. 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.

Moreover, as an organic group which has the epoxy ring which comprises R < ₁ >, R < ₂ >, R < ₃ > and R < ₄ >, what is shown, for example in following formula (3) is mentioned.

  In formula (3), Y is a C1-C8 bivalent organic group. The divalent organic group constituting Y is a linear or branched divalent hydrocarbon group which may have one or more of oxygen, nitrogen and silicon. Among these, 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 an ether bond as a linking group in the main chain are particularly preferable. Moreover, what is Y is a C4-C8 bivalent organic group is also mentioned as an example of a preferable aspect. In this case, Y can be, for example, a linear or branched alkylene group having 4 to 8 carbon atoms. One or more hydrogen atoms in the organic group constituting Y may be substituted with a halogen atom such as fluorine, chlorine, bromine or iodine.

  In this embodiment, it is mentioned as an example of a preferable aspect that the structural unit shown by the said Formula (1) which has an oxetane ring is included in a polymer (a). An example of a more preferable embodiment in which the structural unit represented by the above formula (1) having an oxetane ring and the structural unit represented by the above formula (1) having an epoxy ring are both contained in the polymer (a). As mentioned. Thereby, it can contribute to the balance improvement of a process margin and chemical | medical solution tolerance. In addition, the transparency and the recovery rate can be improved.

  The polymer (a) includes, for example, a structural unit represented by the following formula (4), a structural unit represented by the following formula (5), a structural unit represented by the following formula (6), a structural unit represented by the following formula (7), and the following formula: One or more of the structural units shown in (8) can be further included. As a result, it is possible to improve developability, transparency, durability and the like while improving the balance between the process margin and the chemical resistance.

（式（４）中、Ｒ_５は、水素、炭素数１〜１２のアルキル基、炭素数３〜８のシクロアルキル基、または炭素数６〜１２のアリール基である）

(In Formula (4), R ₅ is hydrogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms)

（式（５）中、Ｒ_６、Ｒ_７およびＲ_８は、それぞれ独立して水素、炭素数１〜１２のアルキル基、炭素数３〜８のシクロアルキル基、または炭素数６〜１２のアリール基である）

(In the formula _{(5), R 6, R} 7 and _{R 8} are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or aryl having 6 to 12 carbon atoms, Base)

（式（６）中、Ｒ_９およびＲ_１０は、それぞれ独立して水素、または炭素数１〜１２の有機基である）

(In Formula (6), R ₉ and R ₁₀ are each independently hydrogen or an organic group having 1 to 12 carbon atoms)

（式（７）中、Ｒ_１１は炭素数１〜１０の有機基である）

(In formula (7), R ₁₁ is an organic group having 1 to 10 carbon atoms)

In the present embodiment, for example, the structural unit represented by the above formula (4), the structural unit represented by the above formula (5), the structural unit represented by the above formula (6), and the structure represented by the above formula (7). More preferably, the polymer (a) contains one or more of the units. Moreover, it is mentioned as an example of an especially preferable aspect that at least the structural unit shown by the said Formula (4) is included in a polymer (a).
When a plurality of structural units represented by the above formula (4) are present in the polymer (a), the structure of each structural unit represented by the above formula (4) can be determined independently. This is the same for the structural unit represented by the above formula (5), the structural unit represented by the above formula (6), and the structural unit represented by the above formula (7).

Examples of the alkyl group having 1 to 12 carbon atoms constituting R ₅ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and pentyl. Group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group. Examples of the cycloalkyl group having 3 to 8 carbon atoms constituting R ₅ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. The aryl group having 6 to 12 carbon atoms constituting the R _5, for example include phenyl group and naphthyl group. One or more hydrogen atoms contained in R ₅ may be substituted with a halogen atom such as fluorine, chlorine, bromine or iodine.

In the present embodiment, in the polymer (a), R ₅ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms. And a structural unit represented by the above formula (4) in which R ₅ is hydrogen. Thereby, it can contribute to the balance improvement of a process margin and chemical | medical solution tolerance. In addition, the transparency can be improved.

Examples of the alkyl group having 1 to 12 carbon atoms constituting R ₆ , R ₇ and R ₈ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, Examples include a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group. Examples of the cycloalkyl group having 3 to 8 carbon atoms constituting R ₆ , R ₇ and R ₈ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. . _The aryl group having 6 to 12 carbon atoms constituting the R 6, _{R 7} and _{R 8,} examples thereof include phenyl and naphthyl. One or more hydrogen atoms contained in R ₆ , R ₇ and R ₈ may be substituted with a halogen atom such as fluorine, chlorine, bromine or iodine. In this embodiment, it is mentioned as an example of a preferable aspect that the structural unit shown to the said Formula (5) whose R < ₈ > is hydrogen is included in a polymer (a).

The organic group having 1 to 12 carbon atoms constituting R ₉ and R ₁₀ is particularly preferably, for example, an organic group containing an epoxy ring or an oxetane ring, or an alkyl group. As the alkyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group Groups, nonyl groups, decyl groups, undecyl groups, and dodecyl groups. Among these, a C3-C12 alkyl group is especially preferable. One or more hydrogen atoms contained in R ₉ and R ₁₀ may be substituted with a halogen atom such as fluorine, chlorine, bromine or iodine.

Examples of the organic group having 1 to 10 carbon atoms constituting R ₁₁ include an organic group containing an epoxy ring or an oxetane ring, or an alkyl group. As the alkyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group Groups, nonyl groups, and decyl groups. One or more hydrogen atoms contained in R ₁₁ may be substituted with a halogen atom such as fluorine, chlorine, bromine or iodine. In the present embodiment, given as an example of it is a preferred embodiment of a structural unit R ₁₁ is represented by the above formula (7) is an organic group containing an epoxy ring or an oxetane ring in the polymer (a).

  In addition, the polymer (a) is a structural unit represented by the above formula (1), a structural unit represented by the above formula (4), and a structural unit represented by the above formula (5) as long as the effects of the present invention are not impaired. And a structural unit represented by the above formula (6), a structural unit represented by the above formula (7), and a structural unit other than the structural unit represented by the above formula (8).

  The polymer (a) includes, for example, a monomer represented by the following formula (9), a monomer represented by the following formula (10), a monomer represented by the following formula (11), a monomer represented by the following formula (12), and anhydrous as a low molecular weight component. One kind or two or more kinds of maleic acid may be contained.

（式（９）中、ｎ、Ｒ_１、Ｒ_２、Ｒ_３およびＲ_４は、上記式（１）において例示したものとすることができる）

(In formula (9), n, R ₁ , R ₂ , R ₃ and R ₄ can be exemplified in the above formula (1)).

（式（１０）中、Ｒ_５は、上記式（４）において例示したものとすることができる）

(In formula (10), R ₅ can be exemplified in the above formula (4)).

（式（１１）中、Ｒ_９およびＲ_１０は、上記式（６）において例示したものとすることができる）

(In formula (11), R ₉ and R ₁₀ may be those exemplified in the above formula (6))

（式（１２）中、Ｒ_１１は、上記式（７）において例示したものとすることができる）

(In the formula (12), R ₁₁ can be exemplified in the above formula (7)).

  In this embodiment, it is preferable that content of the polymer (a) in the photosensitive resin composition is 20 mass% or more with respect to the whole solid content of the photosensitive resin composition, and it is 30 mass% or more. Is more preferable. Thereby, the sclerosis | hardenability and mechanical characteristic of the photosensitive resin composition can be improved more effectively. It can also contribute to improving the balance between process margin and chemical resistance. On the other hand, the content of the polymer (a) in the photosensitive resin composition is preferably 90% by mass or less and more preferably 80% by mass or less with respect to the entire solid content of the photosensitive resin composition. Is preferred. Thereby, the resolution in lithography can be improved. In addition, in this specification, solid content of the photosensitive resin composition refers to the component except the solvent contained in the photosensitive resin composition.

(Photosensitive agent (b))
The photosensitive resin composition can contain, for example, a photosensitive agent (b). Examples of the photosensitive agent (b) include those containing a diazoquinone compound. Examples of the diazoquinone compound used as the photosensitive agent (b) include those exemplified below.

（ｎ２は、１以上５以下の整数である）

(N2 is an integer from 1 to 5)

  In each of the above compounds, Q is any one of the structures (q1), (q2) and (q3) shown below, or a hydrogen atom. However, at least one of Q contained in each compound is any one of the structure (q1), the structure (q2), and the structure (q3). From the viewpoint of the transparency and dielectric constant of the photosensitive resin composition, an o-naphthoquinonediazide sulfonic acid derivative in which Q is the structure (q1) or the structure (q2) is more preferable.

  In the present embodiment, the content of the photosensitive agent (b) in the photosensitive resin composition is preferably 1% by mass or more with respect to the entire solid content of the photosensitive resin composition, and is preferably 5% by mass or more. It is more preferable. On the other hand, the content of the photosensitive agent (b) in the photosensitive resin composition is preferably 40% by mass or less, and preferably 30% by mass or less, based on the entire solid content of the photosensitive resin composition. More preferred. By adjusting the content of the photosensitive agent (b) to such a range, it becomes possible to more effectively improve the balance between reactivity and stability over time in the photosensitive resin composition.

(Crosslinking agent (c))
The photosensitive resin composition may contain the crosslinking agent (c). Thereby, the sclerosis | hardenability of the photosensitive resin composition can be improved and it can contribute to the improvement of the mechanical characteristic of a cured film. The cross-linking agent (c) preferably includes, for example, a compound having a hetero ring as a reactive group, and particularly preferably includes a compound having a glycidyl group or an oxetanyl group. Among these, it is more preferable to include a compound having a glycidyl group from the viewpoint of reactivity with a functional group having active hydrogen such as a carboxyl group or a hydroxyl group.

  Examples of the compound having a glycidyl group used as the crosslinking agent (c) include an epoxy compound. Examples of the epoxy compound include n-butyl glycidyl ether, 2-ethoxyhexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether. Glycidyl ether such as sorbitol polyglycidyl ether, glycidyl ether of bisphenol A (or F), glycidyl ester such as adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester, 3,4-epoxycyclohexylmethyl (3,4) -Epoxycyclohexane) carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl (3,4-epoxy) -6-methylcyclohexane) carboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, dicyclopentanediene oxide, bis (2,3-epoxycyclopentyl) ether, and Celoxide manufactured by Daicel Corporation 2021, celoxide 2081, celoxide 2083, celoxide 2085, celoxide 8000, epoxide GT401, and the like, 2,2 ′-(((((1- (4- (2- (4- (oxiran-2-ylmethoxy) ) Phenyl) propan-2-yl) phenyl) ethane-1,1-diyl) bis (4,1-phenylene)) bis (oxy)) bis (methylene)) bis (oxirane) (eg Techmore VG3101L ) Made by Printec)), Eporai Aliphatic polyglycidyl ethers such as 100MF (manufactured by Kyoeisha Chemical Industry Co., Ltd.) and Epiol TMP (manufactured by NOF Corporation), 1,1,3,3,5,5-hexamethyl-1,5-bis (3 -(Oxiran-2-ylmethoxy) propyl) tri-siloxane (for example, DMS-E09 (manufactured by Gerest)) or the like can be used.

In addition, bisphenols such as LX-01 (manufactured by Daiso Corporation), jER1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 (trade names; manufactured by Mitsubishi Chemical Corporation) A type epoxy resin, bisphenol F type epoxy resin such as jER807 (trade name; manufactured by Mitsubishi Chemical Corporation), jER152, 154 (trade name; manufactured by Mitsubishi Chemical Corporation), EPPN201, 202 (trade name; Japan) Phenolic novolak type epoxy resins such as EOCN102, 103S, 104S, 1020, 1025, 1027 (trade name; manufactured by Nippon Kayaku Co., Ltd.), jER157S70 (trade name; Mitsubishi Chemical Corporation) Cresol novolac type epoxy resin, Araldite CY179, 184 (trade name; Hunts) Advanced Materials), ERL-4206, 4221, 4234, 4299 (trade name; manufactured by Dow Chemical Company), Epicron 200, 400 (trade name; manufactured by DIC Corporation), jER871, 872 (trade name; Mitsubishi) (Chemical Co., Ltd.) and other cyclic aliphatic epoxy resins such as Poly [(2-oxylanyl) -1,2-cyclohexanediol] 2-ethyl-2- (hydroxymethyl) -1,3-propanediol (3: 1), etc. The polyfunctional alicyclic epoxy resin of EHPE-3150 (made by Daicel Corporation) can also be used.
In addition, the photosensitive resin composition in this embodiment can contain 1 type, or 2 or more types of the epoxy compound illustrated above.

  Examples of the compound having an oxetanyl group used as the crosslinking agent (c) include 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-oxetanylmethoxy) biphenyl, ethylene glycol bis (3-ethyl-3 -Oxetanylmethyl) ether, diethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, bis (3-ethyl-3-oxetanylmethyl) diphenoate, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, penta Erythritol tetrakis (3-ethyl-3 Oxetanylmethyl) ether, poly [[3-[(3-ethyl-3-oxetanyl) methoxy] propyl] silasesquioxane] derivatives, oxetanyl silicate, phenol novolac oxetane, 1,3-bis [(3-ethyloxetane 3-yl) methoxy] benzene and the like, but are not limited thereto. These may be used alone or in combination.

  In the present embodiment, the content of the crosslinking agent (c) in the photosensitive resin composition is preferably 1% by mass or more, and preferably 5% by mass or more with respect to the entire solid content of the photosensitive resin composition. It is more preferable. On the other hand, the content of the crosslinking agent (c) in the photosensitive resin composition is preferably 50% by mass or less, and preferably 40% by mass or less, based on the entire solid content of the photosensitive resin composition. More preferred. By adjusting the content of the crosslinking agent (c) to such a range, it is possible to more effectively improve the balance between reactivity and stability over time in the photosensitive resin composition. It can also contribute to improving the balance between process margin and chemical resistance.

(Acid generator (d))
The photosensitive resin composition may contain the acid generator (d). Thereby, the crosslinking reaction of a polymer (a) or a crosslinking agent (c) can be accelerated | stimulated, and the sclerosis | hardenability of the photosensitive resin composition can be improved.

  As the acid generator (d), for example, a photoacid generator that generates acid by light or a thermal acid generator that generates acid by heat can be used.

  The acid generator (d) is, for example, triphenylsulfonium trifluoromethanesulfonate, tris (4-t-butylphenyl) sulfonium-trifluoromethanesulfonate, diphenyl [4- (phenylthio) phenyl] sulfonium tetrakis ( Sulfonium salts such as pentafluorophenyl) borate, diazonium salts such as p-nitrophenyldiazonium hexafluorophosphate, ammonium salts, phosphonium salts, diphenyliodonium trifluoromethanesulfonate, iodonium such as (triccumyl) iodonium-tetrakis (pentafluorophenyl) borate Salts, quinonediazides, diazomethanes such as bis (phenylsulfonyl) diazomethane, 1-phenyl-1- 4-methylphenyl) sulfonyloxy-1-benzoylmethane, sulfonic acid esters such as N-hydroxynaphthalimide-trifluoromethanesulfonate, disulfones such as diphenyldisulfone, tris (2,4,6-trichloromethyl) -s -Compounds such as triazines such as triazine, 2- (3,4-methylenedioxyphenyl) -4,6-bis- (trichloromethyl) -s-triazine, and the like. The photosensitive resin composition in the present embodiment can also contain one or more of the photoacid generators exemplified above.

  The acid generator (d) is a thermal acid generator, for example, SI-45L, SI-60L, SI-80L, SI-100L, SI-110L, SI-150L (manufactured by Sanshin Chemical Industry Co., Ltd.). Aromatic sulfonium salts such as In the present embodiment, the photo acid generator exemplified above and these thermal acid generators can be used in combination.

  The content of the acid generator (d) in the photosensitive resin composition is preferably 0.1% by mass or more and 15% by mass or less, based on the entire solid content of the photosensitive resin composition, and 0.5% by mass. It is more preferable that it is 10% by mass or more. Thereby, the sclerosis | hardenability of the photosensitive resin composition can be improved more effectively. It can also contribute to improving the balance between process margin and chemical resistance.

(Adhesion aid (e))
The photosensitive resin composition may contain the adhesion assistant (e). The adhesion assistant (e) is not particularly limited, but may include a silane coupling agent such as aminosilane, epoxy silane, acrylic silane, mercaptosilane, vinyl silane, ureido silane, or sulfide silane. These may be used alone or in combination of two or more. Among these, it is more preferable to use epoxysilane from the viewpoint of effectively improving the adhesion to other members.
Examples of aminosilanes include bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, and γ-aminopropyl. Methyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N -Β (aminoethyl) γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-amino-propyltrimethoxysilane, and the like. Examples of the epoxy silane include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Examples of the acrylic silane include γ- (methacryloxypropyl) trimethoxysilane, γ- (methacryloxypropyl) methyldimethoxysilane, and γ- (methacryloxypropyl) methyldiethoxysilane. Examples of mercaptosilane include γ-mercaptopropyltrimethoxysilane. Examples of vinyl silane include vinyl tris (β-methoxyethoxy) silane, vinyl triethoxy silane, and vinyl trimethoxy silane. Examples of ureidosilane include 3-ureidopropyltriethoxysilane. Examples of the sulfide silane include bis (3- (triethoxysilyl) propyl) disulfide and bis (3- (triethoxysilyl) propyl) tetrasulfide.

  The content of the adhesion assistant (e) in the photosensitive resin composition is preferably 0.1% by mass or more and 0.5% by mass or more with respect to the entire solid content of the photosensitive resin composition. It is more preferable. On the other hand, the content of the adhesion assistant (e) in the photosensitive resin composition is preferably 20% by mass or less, and preferably 15% by mass or less, based on the entire solid content of the photosensitive resin composition. Is more preferable. By adjusting the content of the adhesion assistant (e) to such a range, it is possible to more effectively improve the adhesion of the cured film formed using the photosensitive resin composition to other members. it can.

(Surfactant (f))
The photosensitive resin composition may contain the surfactant (f). The surfactant (f) includes, for example, a compound containing a fluorine group (for example, a fluorinated alkyl group) or a silanol group, or a compound having a siloxane bond as a main skeleton. In this embodiment, it is more preferable to use a surfactant (f) containing a fluorosurfactant or a silicone surfactant, and it is particularly preferable to use a fluorosurfactant. Examples of the surfactant include Megafac F-554, F-556, and F-557 manufactured by DIC Corporation, but are not limited thereto.

  The content of the surfactant (f) in the photosensitive resin composition is preferably 0.1% by mass or more and 0.2% by mass or more with respect to the entire solid content of the photosensitive resin composition. It is more preferable. On the other hand, the content of the surfactant (f) in the photosensitive resin composition is preferably 3% by mass or less, preferably 2% by mass or less, based on the entire solid content of the photosensitive resin composition. Is more preferable. By adjusting the content of the surfactant (f) to such a range, the flatness of the photosensitive resin composition can be effectively improved. In addition, it is possible to prevent the occurrence of radial striations on the coating film during spin coating.

  In addition, you may add additives, such as antioxidant, a filler, and a sensitizer, in the photosensitive resin composition as needed. The antioxidant can include, for example, one or more selected from the group of phenolic antioxidants, phosphorus antioxidants, and thioether antioxidants. The filler can contain 1 type, or 2 or more types selected from inorganic fillers, such as a silica, for example. The sensitizer is selected from the group of, for example, anthracene, xanthone, anthraquinone, phenanthrene, chrysene, benzpyrene, fluoracene, rubrene, pyrene, indanthrine and thioxanthen-9-ones 1 type, or 2 or more types can be included.

  The photosensitive resin composition may contain a solvent. In this case, the photosensitive resin composition is varnished. 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. One or more of (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and benzyl alcohol can be included. In addition, the solvent which can be used in this embodiment is not limited to these.

In the present embodiment, the light transmittance at a wavelength of 400 nm of the resin film formed using the photosensitive resin composition is preferably 80% or more, and more preferably 85% or more. On the other hand, the upper limit of the transmittance is not particularly limited, but can be 99%, for example. Note that the transmittance of the resin film formed using the photosensitive resin composition can be controlled by appropriately controlling the type and amount of each component contained in the photosensitive resin composition. .
The transmittance can be measured as follows, for example. First, the photosensitive resin composition is spin-coated on a glass substrate and baked on a hot plate at 100 ° C. for 120 seconds to obtain a resin film. Next, the resin film is developed with a 0.5 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 90 seconds, and then rinsed with pure water. Next, the entire surface of the resin film is exposed by g + h + i line at 300 mJ / cm ² and then post-baked by heating in an oven at 230 ° C. for 60 minutes. And the transmittance | permeability in wavelength 400nm of light about this resin film is measured using an ultraviolet-visible light spectrophotometer, and let the numerical value converted into the film thickness of 3 micrometers be transmittance | permeability.

(Electronic device)
Next, the electronic device 100 according to the present embodiment will be described.
The electronic device 100 includes an insulating film 20 that is a permanent film formed of, for example, the above-described photosensitive resin composition. The electronic device 100 according to the present embodiment is not particularly limited as long as it includes an insulating film composed of a cured film of a photosensitive resin composition. For example, a display device having the insulating film 20 as a planarizing film or a microlens. And a semiconductor device having a multilayer wiring structure using the insulating film 20 as an interlayer insulating film.

FIG. 1 is a cross-sectional view illustrating an example of the electronic device 100.
FIG. 1 illustrates the case where the electronic device 100 is a liquid crystal display device and the insulating film 20 is used as a planarization film. An electronic device 100 illustrated in FIG. 1 is provided on, for example, a substrate 10, a transistor 30 provided on the substrate 10, an insulating film 20 provided on the substrate 10 so as to cover the transistor 30, and the insulating film 20. Wiring 40.

  The substrate 10 is, for example, a glass substrate. The transistor 30 is a thin film transistor that constitutes a switching element of a liquid crystal display device, for example. On the substrate 10, for example, a plurality of transistors 30 are arranged in an array. The transistor 30 shown in FIG. 1 includes, for example, a gate electrode 31, a source electrode 32, a drain electrode 33, a gate insulating film 34, and a semiconductor layer 35. The gate electrode 31 is provided on the substrate 10, for example. The gate insulating film 34 is provided on the substrate 10 so as to cover the gate electrode 31. The semiconductor layer 35 is provided on the gate insulating film 34. The semiconductor layer 35 is, for example, a silicon layer. The source electrode 32 is provided on the substrate 10 so that a part thereof is in contact with the semiconductor layer 35. The drain electrode 33 is provided on the substrate 10 so as to be separated from the source electrode 32 and partially in contact with the semiconductor layer 35.

The insulating film 20 functions as a planarization film for eliminating a step due to the transistor 30 and the like and forming a flat surface on the substrate 10. Moreover, the insulating film 20 is comprised with the hardened | cured material of the above-mentioned photosensitive resin composition. The insulating film 20 is provided with an opening 22 that penetrates the insulating film 20 so as to be connected to the drain electrode 33.
A wiring 40 connected to the drain electrode 33 is formed on the insulating film 20 and in the opening 22. The wiring 40 functions as a pixel electrode that constitutes a pixel together with the liquid crystal.
An alignment film 90 is provided on the insulating film 20 so as to cover the wiring 40.

A counter substrate 12 is disposed above one surface of the substrate 10 where the transistor 30 is provided so as to face the substrate 10. A wiring 42 is provided on one surface of the counter substrate 12 facing the substrate 10. The wiring 42 is provided at a position facing the wiring 40. An alignment film 92 is provided on the one surface of the counter substrate 12 so as to cover the wiring 42.
The liquid crystal constituting the liquid crystal layer 14 is filled between the substrate 10 and the counter substrate 12.

The electronic device 100 shown in FIG. 1 can be formed as follows, for example.
First, the transistor 30 is formed over the substrate 10. Next, the photosensitive resin composition is applied to one surface of the substrate 10 on which the transistor 30 is provided by a printing method or a spin coating method, and the insulating film 20 that covers the transistor 30 is formed. Next, the insulating film 20 is exposed to ultraviolet light or the like and developed to pattern the insulating film 20. Thereby, an opening 22 is formed in a part of the insulating film 20. Next, the insulating film 20 is heated and cured. As a result, the insulating film 20 that is a planarizing film is formed on the substrate 10.
Next, a wiring 40 connected to the drain electrode 33 is formed in the opening 22 of the insulating film 20. Thereafter, the counter substrate 12 is disposed on the insulating film 20, and liquid crystal is filled between the counter substrate 12 and the insulating film 20 to form the liquid crystal layer 14.
As a result, the electronic device 100 shown in FIG. 1 is formed.

  It should be noted that the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.

  Next, examples of the present invention will be described.

(Example of monomer synthesis)
In a reaction vessel equipped with a stirrer and a cooler, 700.0 g of dicyclopentadiene and 100.0 g of liquid paraffin are added, and the decomposition product obtained by heating at 160 to 170 ° C. is converted into a cooler (cooling water The mixture was cooled at a temperature of 5 ° C. to obtain cyclopentadiene. Next, 283.2 g of oxetane acrylic (OXE-10, manufactured by Osaka Organic Chemical Industry Co., Ltd.) was placed in another reaction vessel, and 100 g of the cyclopentadiene obtained above was obtained over 3 hours at 20 ° C. Was added successively, followed by stirring for 16 hours at 30 ° C to 35 ° C. Subsequently, the reaction product obtained by this was fractionally purified by a vacuum distillation apparatus using a Vigreux column to obtain a monomer represented by the following formula (13).

^{The 1} H-NMR spectrum and ¹³ C-NMR spectrum were analyzed, and it was confirmed that the obtained monomer had a structure represented by the above formula. Moreover, the obtained monomer was a structural isomer mixture of endo / exo = 78/22. In addition, the measured NMR spectrum data were as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): 0.91 (t, endo-3H), 0.92 (t, exo-3H), 1.29 (d, endo-1H), 1.37-1. 47 (m, 2H), 1.52 (d, exo-1H), 1.73-1.80 (m, 2H), 1.90-1.97 (m, 1H), 2.26-2. 30 (m, exo-1H), 2.92 (brs, 1H), 2.98-3.03 (m, endo-1H), 3.05 (brs, exo-1H), 3.23 ( s, endo-1H), 4.16 (dd, endo-2H), 4.23 (dd, exo-2H), 4.40 (d, endo-2H), 4.41 (d, exo-2H) 4.46 (d, endo-2H), 4.49 (dd, exo-2H), 5.92 (dd, endo-1H), 6 11-6.16 (m, exo-2H), 6.21 (dd, endo-1H).
¹³ C-NMR (100 MHz, CDCl ₃ ): 8.0, 26.9, 29.1, 30.3, 41.6, 42.4, 42.6, 42.6, 43.1, 43.3 , 45.7, 46.3, 46.6, 49.6, 65.9, 66.2, 77.8, 77.9, 132.1, 135.6, 137.9, 138.0, 174 .7, 176.2 ppm.

(Polymer synthesis)
(Synthesis Example 1)
First, the monomer (11.8 g, 50 mmol) obtained by the above synthesis example, maleic anhydride (2.5 g, 26.6 mmol), and N-cyclohexylmaleimide (4.5 g, 25 mmol) were placed in a sealable reaction vessel. 0.1 mmol). Furthermore, 6.9 g of MEK in which V-601 (1.15 g, 5 mmol) was dissolved was added to the reaction vessel, and stirred and dissolved. Next, after removing dissolved oxygen in the system by nitrogen bubbling, the vessel was sealed and reacted at 70 ° C. for 16 hours. The reaction mixture was then cooled to room temperature and 36 g of MEK was added and diluted. The diluted solution was poured into a large amount of hexane to precipitate a polymer. Next, the polymer was collected by filtration, further washed with hexane, and then vacuum-dried at 30 ° C. for 16 hours. At this time, the yield of the polymer was 16.8 g, and the yield was 90%. Next, 2.0 g of the obtained polymer was dissolved in 8.0 g of MEK, dinormal butylamine (1.5 g, 11.6 mmol) was added, and the mixture was reacted at 70 ° C. for 3 hours. Next, formic acid (1.1 g, 23.9 mmol) was added for neutralization, and washing with water was repeated three times to remove the neutralized salt. The reaction product thus obtained was poured into a large amount of hexane to precipitate a polymer. Next, the polymer was collected by filtration, further washed with hexane, and then vacuum-dried at 30 ° C. for 16 hours. The polymer yield was 2.5 g. In addition, the polymer had a weight average molecular weight Mw of 6,950 and a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.53.
The obtained polymer had a structure represented by the following formula (14).

As the weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polymer, a polystyrene equivalent value obtained from a calibration curve of standard polystyrene (PS) obtained by GPC measurement was used. The measurement conditions are as follows.
Gel permeation chromatography device HLC-8320GPC manufactured by Tosoh Corporation
Column: Tosoh Corporation TSK-GEL Supermultipore HZ-M
Detector: RI detector for liquid chromatogram Measurement temperature: 40 ° C
Solvent: THF
Sample concentration: 2.0 mg / milliliter In addition, the measurement conditions of a weight average molecular weight (Mw) and a number average molecular weight (Mn) are the same in the synthesis examples 2-6 mentioned later.

(Synthesis Example 2)
In a sealable reaction vessel, the monomer obtained by the above synthesis example (10.8 g, 45.8 mmol), norbornene carboxylic acid (11.92 g, 91.7 mmol), methyl glycidyl ether norbornene (57.6 g, 320 mmol) , Maleimide (28.88 g, 297.7 mmol), and N-cyclohexylmaleimide (16.32 g, 91.2 mmol) were weighed. Further, 58.4 g of PGME in which V-601 (8.4 g, 36.5 mmol) was dissolved was added to the reaction vessel, and stirred and dissolved. Next, after the dissolved oxygen in the system was removed by nitrogen bubbling, the container was sealed and reacted at 70 ° C. for 16 hours. The reaction mixture was then cooled to room temperature and diluted by adding 226 g of THF. The diluted solution was poured into a large amount of methanol to precipitate a polymer. Next, the polymer was collected by filtration, further washed with methanol, and then vacuum-dried at 30 ° C. for 16 hours. The polymer yield was 64.6 g and the yield was 51%. The polymer had a weight average molecular weight Mw of 13,500 and a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.71.
The obtained polymer had a structure represented by the following formula (15).

(Synthesis Example 3)
In a reaction vessel equipped with a stirrer and a condenser, the monomer (30.3 g, 128 mmol), maleimide (17.4 g, 179 mmol) obtained by the above synthesis example, N-cyclohexylmaleimide (13.8 g, 76.9 mmol). ), Ethyl oxetane vinyl ether (14.5 g, 103 mmol), butanediol monovinyl monoglycidyl ether (4.1 g, 25.6 mmol). Furthermore, 77.6 g of THF in which V-601 (2.36 g, 10.3 mmol) was dissolved was added to the reaction vessel, and stirred and dissolved. Next, the dissolved oxygen in the system was removed by nitrogen bubbling, and then kept at 60 ° C. in a nitrogen atmosphere and reacted for 5 hours. The reaction mixture was then cooled to room temperature and diluted by adding 106.7 g of THF. The diluted solution was poured into a large amount of hexane to precipitate a polymer. Next, the polymer was collected by filtration, further washed with hexane, and then vacuum-dried at 30 ° C. for 16 hours. The yield of the polymer was 61.8 g, and the yield was 77%. The polymer had a weight average molecular weight Mw of 10,330 and a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 2.35.
The obtained polymer had a structure represented by the following formula (16).

(Synthesis Example 4)
In a reaction vessel equipped with a stirrer and a condenser, the monomers (1.18 g, 5 mmol), maleimide (2.18 g, 22.5 mmol), N-cyclohexylmaleimide (4.92 g, 27) obtained in the above synthesis example were used. 0.5 mmol), norbornene carboxylic acid (2.60 g, 20.0 mmol), methyl glycidyl ether norbornene (3.6 g, 20.0 mmol), and dibutyl fumaric acid (1.14 g, 5 mmol) were weighed. Furthermore, 8.9 g of propylene glycol monomethyl ether acetate in which V-601 (0.92 g, 4.0 mmol) was dissolved was added to the reaction vessel, and stirred and dissolved. Next, after removing dissolved oxygen in the system by nitrogen bubbling, the reaction was held at 70 ° C. in a nitrogen atmosphere for 5 hours. The reaction mixture was then cooled to room temperature and diluted with 30 g of MEK. The diluted solution was poured into a large amount of hexane to precipitate a polymer. Next, the polymer was collected by filtration, further washed with hexane, and then vacuum-dried at 30 ° C. for 16 hours. The polymer yield was 13.4 g and the yield was 86%. The polymer had a weight average molecular weight Mw of 8,800 and a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 2.19.
The obtained polymer had a structure represented by the following formula (17).

(Synthesis Example 5)
To a suitably sized reaction vessel equipped with stirrer and condenser, maleic anhydride (MA, 78.5 g, 801 mmol), 2-norbornene (NB, 75.3 g, 801 mol) and dimethyl 2,2′-azobis ( 2-Methylpropionate) (18.4 g, 80 mmol) was weighed and dissolved in methyl ethyl ketone (MEK, 300 g) and toluene (25 g). The solution was purged with nitrogen for 10 minutes to remove oxygen, and then heated at 70 ° C. for 16 hours with stirring. Thereafter, MEK (250 g) was added to the solution, and then poured into a large amount of methanol to precipitate a polymer. The polymer was collected by filtration and further washed with methanol, and then vacuum dried at 30 ° C. for 16 hours. The yield of polymer was 150 g. Next, 5.0 g of the obtained polymer was dissolved in 25.0 g of oxetane alcohol (manufactured by Toagosei Co., Ltd., OXT-101) and 25 g of pyridine, and reacted at 70 ° C. for 16 hours. Then, formic acid 128g was added and neutralized. Further, after adding water and washing with water three times, the reaction solution was poured into a large amount of hexane to precipitate a polymer. The polymer was collected by filtration, further washed with hexane, and then vacuum dried at 30 ° C. for 16 hours. The yield of polymer was 5.5 g. The polymer had a weight average molecular weight Mw of 5,900 and a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.96.
The obtained polymer had a structure represented by the following formula (18).

(Synthesis Example 6)
In a suitably sized reaction vessel equipped with stirrer and condenser, maleic anhydride (MA, 122.4 g, 1.25 mol), 2-norbornene (NB, 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 (MEK, 150.8 g) and toluene (77.7 g). The dissolved solution was purged with nitrogen for 10 minutes to remove oxygen, and then heated at 60 ° C. for 16 hours with stirring. Thereafter, MEK (320 g) was added to the solution, and this was added with sodium hydroxide (12.5 g, 0.31 mol), butanol (463.1 g, 6.25 mol), toluene (480 g). Added to the suspension and mixed at 45 ° C. for 3 hours. The mixture is cooled to 40 ° C., treated with formic acid (88% by weight aqueous solution, 49.0 g, 0.94 mol), protonated, and then MEK and water are added to separate the aqueous layer. Inorganic residues were removed. Subsequently, methanol and hexane were added and the organic layer was separated to remove unreacted monomers. Further, PGMEA was added, and methanol and butanol in the system were distilled off under reduced pressure until the residual amount was less than 1%. Thereafter, the reaction solution was heated to 125 ° C. and reacted until the alkali dissolution time reached the optimum range. As a result, 1107.7 g of a 20% by mass polymer solution was obtained (GPC Mw = 13,700, Mn = 7,400).
The obtained polymer had a structure represented by the following formula (19).

(Preparation of photosensitive resin composition)
About each of Examples 1-5 and Comparative Examples 1-2, the varnish-like photosensitive resin composition was adjusted as follows. First, each component blended according to Table 1 was dissolved in a mixed solvent of ethyl lactate: diethylene glycol methyl ethyl ether = 70: 30 so as to have a solid content of 20%. Subsequently, the mixed solution obtained by this was filtered with the 0.2-micrometer PTFE filter, and the photosensitive resin composition was prepared. Details of each component in Table 1 are as follows.

(A) Polymer polymer 1: Polymer polymer obtained by Synthesis Example 1 above: Polymer polymer 3 obtained by Synthesis Example 2 above: Polymer polymer obtained by Synthesis Example 3 above: Obtained by Synthesis Example 4 above Polymer polymer 5: Polymer polymer obtained in Synthesis Example 5 above: Polymer obtained in Synthesis Example 6 above

(B) Photosensitizer Photosensitive agent 1: PA-28, Daitokemix Co., Ltd. photosensitizer 2: PA-15, Daitokemix Co., Ltd. photosensitizer 3: PA-3, manufactured by Daitokemix Co., Ltd. PA-28, PA-15 and PA-3 are both 4,4 ′-(1- {4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl} ethylidene) bisphenol and 1,2-naphthoquinonediazide. It is an esterified product with -5-sulfonyl chloride, which has different esterification rates.

(C) Crosslinking agent compound 1: Compound represented by the following formula (20) (VG3101L, manufactured by Printec Co., Ltd.)
Compound 2: Bisphenol A type epoxy compound (LX-01, manufactured by Daiso Corporation)
Compound 3: Alicyclic epoxy compound (CEL2081, manufactured by Daicel Corporation)

(D) Acid generator Acid generator 1: 1-naphthylmethylmethyl-p-hydroxyphenylsulfonium hexafluoroantimonate (SI-60L, manufactured by Sanshin Chemical Industry Co., Ltd.)
Acid generator 2: diphenyl [4- (phenylthio) phenyl] sulfonium tetrakis (pentafluorophenyl) borate (CPI-110B, manufactured by San Apro Co., Ltd.)

(E) Adhesion aid Adhesion aid 1: 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Silicone Co., Ltd.)
Adhesion aid 2: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303, manufactured by Shin-Etsu Silicone Co., Ltd.)

(F) Surfactant Fluorosurfactant (F-557, manufactured by DIC Corporation)

(PED (Post Exposure Delay))
About each Example and each comparative example, PED of the photosensitive resin composition obtained as follows was measured. First, the photosensitive resin composition is spin-coated on a 1737 glass substrate manufactured by Corning Inc. having a length of 100 mm and a width of 100 mm (rotation speed: 500 to 2500 rpm), and prebaked at 100 ° C. for 120 seconds using a hot plate. Thus, a resin film having a thickness of about 3.0 μm was obtained. Here, two samples (first sample and second sample) obtained by this were prepared. Next, using a mask having a mask pattern with a width of 5 μm, the first sample and the second sample were irradiated with g + h + i line by a g + h + i line mask aligner (manufactured by Canon Inc., PLA-501F (super high pressure mercury lamp)). The exposure process was performed. Here, the cumulative amount of light pattern width W ₁ of after development of the first sample to be described later is 5 [mu] m, was subjected to exposure processing for the first sample and the second sample.

The first sample was immersed in a developer (0.5 wt% TMAH) for 90 seconds without exposure after the exposure, and then rinsed with pure water. For the second sample, after leaving it in the yellow room (using a HEPA filter) maintained for 6 hours after exposure, at an air temperature of 23 ± 1 ° C. and a humidity of 40 ± 5%, a developer (0.5 wt% TMAH) And then rinsed with pure water. At this time, assuming that the width of the pattern corresponding to the mask pattern formed on the first sample is W ₁ and the width of the pattern corresponding to the mask pattern formed on the second sample is W ₂ , (W ₁ −W ₂ ) / W ₁ × 100 (%) was defined as PED.

(Swelling rate, recovery rate)
About each Example and each comparative example, the swelling rate and recovery rate of the photosensitive resin composition were measured as follows. First, the photosensitive resin composition is spin-coated on a 1737 glass substrate manufactured by Corning Inc. having a length of 100 mm and a width of 100 mm (rotation speed: 500 to 2500 rpm), and prebaked at 100 ° C. for 120 seconds using a hot plate. Thus, a resin film having a thickness of about 3.0 μm was obtained. Next, the resin film was immersed in a developing solution (0.5 wt% TMAH) at 23 ° C. for 90 seconds for development treatment, and then rinsed with pure water. Next, the entire surface of the resin film was exposed using a g + h + i line mask aligner (manufactured by Canon Inc., PLA-501F (extra-high pressure mercury lamp)) so that the integrated light amount was 300 mJ / cm ² . .

Next, heat treatment (first heat treatment) was performed on the resin film in an oven at 230 ° C. for 60 minutes. The cured film thus obtained was immersed in a mixed solution (TOK106, manufactured by Tokyo Ohka Kogyo Co., Ltd.) of monoethanolamine and dimethyl sulfoxide (= 7: 3) at 70 ° C. for 15 minutes, and then washed with pure water. Rinse for 2 seconds. At this time, the film thickness after the first heat treatment of the resin film is defined as the first film thickness, and the film thickness after immersion in the mixed solution of monoethanolamine and dimethyl sulfoxide is defined as the second film thickness.
[(Second film thickness-first film thickness) / (first film thickness)] × 100 (%)
Was defined as the swelling ratio. Moreover, the resin film after being immersed in the mixed solution of monoethanolamine and dimethyl sulfoxide was heated in an oven at 230 ° C. for 15 minutes, and the film thickness after heating (third film thickness) was measured. At this time,
[(Third film thickness) / (first film thickness)] × 100 (%)
Was the recovery rate.

(Transmittance)
The transmittance of each example and each comparative example was measured as follows. First, the photosensitive resin composition is spin-coated on a 1737 glass substrate manufactured by Corning Inc. having a length of 100 mm and a width of 100 mm (rotation speed: 500 to 2500 rpm), and prebaked at 100 ° C. for 120 seconds using a hot plate. Thus, a resin film having a thickness of about 3.0 μm was obtained. Next, the resin film was immersed in a developer (0.5 wt% TMAH) for 90 seconds, and then rinsed with pure water. Next, the entire surface of the g + h + i line was exposed using a g + h + i line mask aligner (manufactured by Canon Inc., PLA-501F (extra-high pressure mercury lamp)) so that the integrated light amount was 300 mJ / cm ² . Next, a thermosetting treatment was performed on the resin film in an oven at 230 ° C. for 60 minutes. At this time, the film thickness of the resin film was about 2.5 μm. Next, the transmittance of the resin film with respect to light having a wavelength of 400 nm was measured using an ultraviolet-visible light spectrophotometer. In Table 1, values converted into transmittance with a film thickness of 3 μm are shown.

(Manufacturing stability evaluation 1)
About each Example and each comparative example, manufacturing stability was evaluated as follows.
First, a glass substrate having a thin film transistor formed on one side was prepared. Next, after applying the photosensitive resin composition obtained above on one surface of the glass substrate to form a resin film, lithography is performed on this resin film to form an opening pattern connected to the electrode of the thin film transistor did. Next, the resin film was subjected to curing treatment by heating and chemical treatment, and this was used as a sample. At the time of sample preparation, the design value of the opening diameter of the opening pattern was set to 5 μm, and the design value of the film thickness of the resin film after chemical treatment was set to 10 μm. Subsequently, the opening diameter of the obtained opening pattern and the film thickness of the resin film were measured. Here, the production stability was evaluated as follows.
○: Both aperture diameter and film thickness were as designed values. Δ: At least one of the aperture diameter and film thickness deviated from the design values to the extent that there was no problem with the product. Deviation from the design value occurred to the extent that it can be judged as defective in at least one

(Manufacturing stability evaluation 2)
About each Example and each comparative example, manufacturing stability was evaluated as follows.
First, a glass substrate having a plurality of thin film transistors formed on one surface was prepared. Next, after applying the photosensitive resin composition obtained above on one surface of the glass substrate to form a resin film, lithography is performed on the resin film, and a plurality of electrodes respectively connected to the electrodes of each thin film transistor An opening pattern was formed and used as a sample. At this time, the design values of the opening diameters of the plurality of opening patterns were all set to 5 μm. Ten samples were prepared, and the opening pattern of each sample was observed. The ten samples had different times from the start of exposure to the start of development in the lithography process. Here, the production stability was evaluated as follows.
○: Open patterns as designed values were obtained in all samples. Δ: Open patterns with deviations from design values to the extent that they do not cause product problems occurred in one or more samples. An opening pattern that has deviated from the design value to the extent possible can occur in one or more samples.

  In Table 1, among the numerical values indicating the blending amount of each component contained in the photosensitive resin composition, the numerical values outside the parentheses indicate the mass (g) of each component, and the numerical values within the parentheses indicate the total amount of the photosensitive resin composition. The blending ratio (mass%) of each component when the solid content (that is, the component excluding the solvent) is 100 mass% is shown.

  As shown in Table 1, in each of Examples 1 to 5, PED was 10% or less, and the swelling ratio was 20% or less. About the photosensitive composition which concerns on such an Example, it was confirmed that the outstanding manufacturing stability is realizable. Moreover, in Examples 1-5, it turns out that the favorable result is obtained also about the transmittance | permeability and the recovery rate.

  This application claims the priority on the basis of Japanese application Japanese Patent Application No. 2014-058119 for which it applied on March 20, 2014, and takes in those the indications of all here.

Claims (5)

A photosensitive resin composition used to form a permanent film,
Including a polymer having a cyclic olefin structural unit;
PED measured under the following conditions (A) is 10% or less,
The photosensitive resin composition whose swelling rate measured by the following conditions (B) is 20% or less.
<Condition (A)>
A resin film obtained by pre-baking the photosensitive resin composition at 100 ° C. for 120 seconds is exposed by irradiating g + h + i rays using a mask having a mask pattern with a width of 5 μm. Next, the resin film is developed by immersing it in a 0.5 mass% tetramethylammonium hydroxide aqueous solution maintained at a liquid temperature of 23 ± 1 ° C. for 90 seconds. At this time, the width of the pattern corresponding to the mask pattern of the sample developed immediately after exposure was set to W ₁ (= 5 μm), and the temperature was maintained at 23 ± 1 ° C. and humidity 40 ± 5% for 6 hours after exposure. The width of the pattern corresponding to the mask pattern of the sample developed after being placed in the room is W ₂ , and (W ₁ −W ₂ ) / W ₁ × 100 (%) is PED.
<Condition (B)>
The resin film obtained by pre-baking the photosensitive resin composition at 100 ° C. for 120 seconds was developed with a 0.5 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 90 seconds, Rinse with water. Next, the entire surface of the resin film is exposed with g + h + i line at 300 mJ / cm ² , and then heat treatment is performed at 230 ° C. for 60 minutes. Next, the resin film is immersed in a mixed solution of monoethanolamine and dimethyl sulfoxide (= 7: 3) at 70 ° C. for 15 minutes. At this time, the film thickness of the resin film after the heat treatment is a first film thickness, and the film thickness after immersion in the mixed solution is a second film thickness.
[(Second film thickness−first film thickness) / (first film thickness)] × 100 (%) is defined as a swelling ratio. In the photosensitive resin composition of Claim 1,
The photosensitive resin composition whose recovery rate measured on condition of the following (C) is 97% or more and 103% or less.
<Condition (C)>
The resin film obtained by pre-baking the photosensitive resin composition at 100 ° C. for 120 seconds was developed with a 0.5 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 90 seconds, Rinse with water. Next, the entire surface of the resin film is exposed with g + h + i line at 300 mJ / cm ² , and then a first heat treatment is performed at 230 ° C. for 60 minutes. Next, the resin film is immersed in a mixed solution of monoethanolamine and dimethyl sulfoxide (= 7: 3) at 70 ° C. for 15 minutes. Next, a second heat treatment is performed on the resin film at 230 ° C. for 15 minutes. At this time, the film thickness after the first heat treatment of the resin film is the first film thickness, the film thickness after the second heat treatment is the third film thickness,
[(Third film thickness) / (first film thickness)] × 100 (%) is defined as a recovery rate. In the photosensitive resin composition of Claim 1 or 2,
The polymer is a photosensitive resin composition containing at least one of an oxetane group and an epoxy group. In the photosensitive resin composition as described in any one of Claims 1-3,
Film thickness obtained by pre-baking the photosensitive resin composition at 100 ° C. for 120 seconds, irradiating g + h + i rays at 300 mJ / cm ² and performing heat treatment at 230 ° C. for 60 minutes. A photosensitive resin composition having a transmittance of 80% or more with respect to light having a wavelength of 400 nm of a 3 μm resin film.   An electronic device provided with the cured film of the photosensitive resin composition as described in any one of Claims 1-4.

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