JP2014232233A - Photosensitive resin composition and electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition exhibiting an excellent balance between chemical resistance and other characteristics demanded for a photosensitive resin composition, and to provide an electronic device having the photosensitive resin composition.SOLUTION: The photosensitive resin composition comprises a polymer (first polymer) expressed by formula (1) shown below, a first crosslinking agent that crosslinks with the polymer, an acrylic resin as a second crosslinking agent having a reactive group that crosslinks with the polymer or the first crosslinking agent, and a photosensitizer. In formula (1), R, R, Rand Reach independently represent hydrogen or an organic group having 1 to 30 carbon atoms; and A represents a structural unit derived from maleic acid anhydride.

Description

  The present invention relates to a photosensitive resin composition and an electronic device.

  A photolithography technique is used to form a fine circuit pattern such as a semiconductor integrated circuit. In the photolithography technique, a photosensitive resin composition is used to form a resist pattern. For example, Patent Document 1 discloses a photosensitive resin composition containing a polymer and a photosensitive agent. And it is disclosed that the polymer has a unit composed of a cyclic aliphatic hydrocarbon skeleton and a unit derived from maleic anhydride, and hydrolyzes the acid anhydride ring of the unit derived from maleic anhydride. Yes.

Japanese Patent Laid-Open No. 2-146045

In recent years, the use of a photosensitive resin composition for an interlayer insulating film of a semiconductor device or a planarizing film covering a TFT electrode of a liquid crystal display device has been studied.
In this case, the photosensitive resin composition may be immersed in a predetermined solvent during the manufacturing process of the product. Therefore, the photosensitive resin composition is required to have improved chemical resistance that does not easily change its film thickness even when immersed in a solvent.
The photosensitive resin composition of Patent Document 1 described above does not have sufficient chemical resistance.

In order to improve chemical resistance, the present inventor has conceived that a photosensitive resin composition contains a crosslinking agent that crosslinks with a polymer. However, when the chemical resistance is increased simply by increasing the amount of the crosslinking agent, other characteristics required for the photosensitive resin composition, such as the flexibility of the cured film of the photosensitive resin composition, may deteriorate. all right.
The present invention provides a photosensitive resin composition having an excellent balance between chemical resistance and other characteristics required for a photosensitive resin composition.

（式（１）中、ｌおよびｍはポリマー中におけるモル含有率を示し、ｌ＋ｍ＝１であり、ｎは０、１または２である。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、Ａは下記式（２ａ）、（２ｂ）、（２ｃ）または（２ｄ）により示される構造単位である）

（式（２ａ）および式（２ｂ）中、Ｒ_５、Ｒ_６およびＲ_７は、それぞれ独立して炭素数１〜１８の有機基である） According to the present invention,
A polymer represented by the following formula (1):
A first crosslinking agent that crosslinks with the polymer;
An acrylic resin that is a second cross-linking agent having a reactive group that cross-links with the polymer or the first cross-linking agent;
There is provided a photosensitive resin composition containing a photosensitive agent.

(In formula (1), l and m represent the molar content in the polymer, l + m = 1, and 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 30 carbon atoms, and A is a structural unit represented by the following formula (2a), (2b), (2c) or (2d))

(In Formula (2a) and Formula (2b), R ₅ , R ₆ and R ₇ are each independently an organic group having 1 to 18 carbon atoms)

  According to this invention, while using an acrylic resin as a 2nd crosslinking agent, the 1st crosslinking agent different from a 2nd crosslinking agent is used. By appropriately selecting a first cross-linking agent different from the second cross-linking agent, a photosensitive resin composition having an excellent balance between chemical resistance and other characteristics than chemical resistance can be obtained.

  Moreover, according to this invention, an electronic apparatus provided with the cured film of the photosensitive resin composition mentioned above can also be provided.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition excellent in balance with chemical resistance and the other characteristic calculated | required by the photosensitive resin composition, and the electronic device which has this photosensitive resin composition are provided.

It is sectional drawing which shows an example of the electronic device which concerns on this embodiment. It is sectional drawing which shows an example of the electronic device which concerns on this embodiment.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same components are denoted by the same reference numerals, and detailed description thereof is appropriately omitted so as not to overlap.
First, the outline | summary of the photosensitive resin composition of this embodiment is demonstrated.
The photosensitive resin composition of the present embodiment is
A polymer represented by the following formula (1) (first polymer);
A first crosslinking agent that crosslinks with the polymer;
An acrylic resin that is a second cross-linking agent having a reactive group that cross-links with the polymer or the first cross-linking agent;
And a photosensitizer.

（式（１）中、ｌおよびｍはポリマー中におけるモル含有率を示し、ｌ＋ｍ＝１であり、ｎは０、１または２である。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、Ａは下記式（２ａ）、（２ｂ）、（２ｃ）または（２ｄ）により示される構造単位である）

（式（２ａ）および式（２ｂ）中、Ｒ_５、Ｒ_６およびＲ_７は、それぞれ独立して炭素数１〜１８の有機基である）

(In formula (1), l and m represent the molar content in the polymer, l + m = 1, and 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 30 carbon atoms, and A is a structural unit represented by the following formula (2a), (2b), (2c) or (2d))

(In Formula (2a) and Formula (2b), R ₅ , R ₆ and R ₇ are each independently an organic group having 1 to 18 carbon atoms)

  As the second crosslinking agent, an acrylic resin is used, and a first crosslinking agent different from the second crosslinking agent is used. By appropriately selecting a first cross-linking agent different from the second cross-linking agent, a photosensitive resin composition having an excellent balance between chemical resistance and other characteristics than chemical resistance can be obtained.

(First polymer)
The 1st polymer which concerns on this embodiment is a polymer mentioned above, and is comprised with the copolymer shown by following formula (1).

In the formula (1), l and m represent molar contents (molar ratio) in the first polymer, and l + m = 1, 0.4 ≦ l ≦ 0.6, 0.4 ≦ m ≦ 0.6 is there. 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 30 carbon atoms. R ₁ , R ₂ , R ₃ and R ₄ may be the same as or different from each other.
A is a structural unit represented by the following formula (2a), (2b), (2c) or (2d). The copolymer represented by the above formula (1) includes one or more structural units A selected from the following formulas (2a), (2b), (2c) and (2d). In this embodiment, it is preferable that at least one or more structural units A selected from the following formulas (2a), (2b) and (2c) are included.

式（２ａ）および式（２ｂ）中、Ｒ_５、Ｒ_６およびＲ_７は、それぞれ独立して炭素数１〜１８の有機基である。

In formula (2a) and formula (2b), R ₅ , R ₆ and R ₇ are each independently an organic group having 1 to 18 carbon atoms.

  In the present embodiment, the copolymer represented by the above formula (1) preferably includes the structural unit A represented by the above formula (2a) and the structural unit A represented by the above formula (2c). Preferably includes the structural unit A represented by (2b). In this case, as will be described later, the acid value of the first polymer can be easily adjusted by adjusting the amount of base used in the ring-opening step or by heat treatment (DR step) after the monomer removal step. Therefore, it becomes easy to adjust the solubility of the film made of the photosensitive resin composition containing the first polymer in the alkaline developer in the photolithography process.

Any of the organic groups constituting R ₁ , R ₂ , R _3, and R ₄ may have no acidic functional group. Thereby, control of the acid value in the first polymer can be facilitated. Further, the organic group constituting R ₁ , R ₂ , R ₃ and R ₄ may contain any one or more of O, N, S, P and Si in the structure.

In this 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, a cycloalkyl group, And heterocyclic groups, and can be selected from these.
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, and can be selected from these. 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, 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. Examples of the heterocyclic group include an epoxy group and an oxetanyl group.
In addition, the film forming property of the film | membrane which consists of the photosensitive resin composition containing a 1st polymer can be improved by including an alkyl group as R < ₁ >, R < ₂ >, R < ₃ > or R < ₄ >. In addition, by including an aryl group as R ₁ , R ₂ , R _3, or R ₄ , a film made of the photosensitive resin composition containing the first polymer is subjected to development using an alkaline developer in the lithography process. Film loss can be suppressed.

Furthermore, in the alkyl group, alkenyl group, alkynyl group, alkylidene group, aryl group, aralkyl group, alkaryl group, cycloalkyl group, and heterocyclic group described above, one or more hydrogen atoms may be substituted with halogen atoms. Good. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Among these, a haloalkyl group in which one or more hydrogen atoms of the alkyl group are substituted with a halogen atom is preferable. When at least one of R ₁ , R ₂ , R _3, and R ₄ is a haloalkyl group to form a photosensitive resin composition using the first polymer, the photosensitive resin composition The dielectric constant can be reduced.
In addition, from the viewpoint of increasing the light transmittance of the film including the first polymer, any of R ₁ , R ₂ , R ₃ and R ₄ is preferably hydrogen, and in particular, R ₁ , R ₂ , R ₃ and R ₄ are all preferably hydrogen.

The organic group having 1 to 18 carbon atoms constituting R ₅ , R ₆ and R ₇ may contain any one or more of O, N, S, P and Si in the structure. The organic group constituting R _5, R ₆ and R _7, can be made free of acid functionality. Thereby, control of the acid value in the first polymer can be facilitated.

In this embodiment, examples of the organic group constituting R ₅ , 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, a cycloalkyl group, and a heterocyclic ring. Groups, which can be selected from these. Here, 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 Groups, octyl groups, nonyl groups, and decyl groups. 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, 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. Examples of the heterocyclic group include an epoxy group and an oxetanyl group.

  Furthermore, in the alkyl group, alkenyl group, alkynyl group, alkylidene group, aryl group, aralkyl group, alkaryl group, cycloalkyl group, and heterocyclic group described above, one or more hydrogen atoms may be substituted with halogen atoms. Good. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Among these, a haloalkyl group in which one or more hydrogen atoms of the alkyl group are substituted with a halogen atom is preferable.

The copolymer represented by the above formula (1) includes, for example, a repeating unit derived from a norbornene type monomer represented by the following formula (3), a repeating unit derived from maleic anhydride represented by the following formula (4), and It is preferable that is an alternating copolymer in which are alternately arranged. The copolymer represented by the above formula (1) may be a random copolymer or a block copolymer.
The repeating unit derived from maleic anhydride shown in the following formula (4) is a structural unit represented by A in the above formula (1). In addition, the 1st polymer may contain the monomer shown by following formula (3) and (4) as a low molecular weight component.

式（３）中、ｎは０、１または２であり、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の有機基である。

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

The first polymer in the present embodiment preferably has an acid value of, for example, 15 mgKOH / g polymer or more and 65 mgKOH / g polymer or less.
The acid value of the first polymer is measured, for example, according to JIS K 2501, as follows. First, the titration solvent in which the synthesized first polymer is dissolved is titrated using an N / 10 KOH aqueous solution so that the pH is 7.0. Based on the amount of KOH required for this titration, the acid value of the polymer (mg of KOH per 1 g of resin) is calculated using the following formula.
Acid value = Titration (ml) × KOH factor f × 0.1 × 56.1 / Amount of polymer (solid)

In the present embodiment, the acid value of the first polymer is an index of the amount of carboxyl groups derived from the structural unit represented by the formula (2a). That is, the amount of carboxyl groups in the first polymer can be adjusted by controlling the acid value of the first polymer. Therefore, by controlling the acid value of the first polymer, it is possible to adjust the dissolution rate of the first polymer in the alkaline solution, which varies due to the amount of the carboxyl group.
In the photolithography process, it is important to adjust the dissolution rate in an alkali developer in order to achieve desired patterning performance. By setting the acid value of the first polymer in the above range, it is possible to realize an alkali dissolution rate of the photosensitive resin composition particularly suitable for patterning of the permanent film.

In the molecular weight distribution curve obtained by GPC (Gel Permeation Chromatography), for example, the first polymer in the present embodiment preferably has a peak area of 1% or less of the total molecular weight of 1000 or less.
The present inventor has found that, by reducing the amount of the low molecular weight component in the first polymer, the deformation of the pattern at the time of curing can be suppressed for the film formed by the first polymer. For this reason, by making the ratio of the peak area at a molecular weight of 1000 or less in the molecular weight distribution curve obtained by GPC within the above range, the pattern shape of the film made of the photosensitive resin composition containing the first polymer is made favorable. be able to. With respect to an electronic device including the film as a permanent film, the operation reliability can be improved.
In addition, the minimum of the quantity of the low molecular weight component in a 1st polymer is not specifically limited. However, the 1st polymer in this embodiment accept | permits the case where the peak area in molecular weight 1000 or less is 0.01% or more of the whole in the molecular weight distribution curve obtained by GPC.

The first polymer in the present embodiment preferably has, for example, Mw (weight average molecular weight) / Mn (number average molecular weight) of 1.5 or more and 2.5 or less. Mw / Mn is a degree of dispersion indicating the width of the molecular weight distribution.
The present inventor has found that, by controlling the molecular weight distribution in the first polymer within a certain range, the deformation of the pattern at the time of curing can be suppressed for the film formed by the first polymer. For this reason, the pattern shape of the film | membrane which consists of the photosensitive resin composition containing a 1st polymer can be made favorable by making Mw / Mn of a 1st polymer into the said range. Such an effect is particularly noticeable when the low molecular weight component of the first polymer is simultaneously reduced as described above.
The Mw (weight average molecular weight) of the first polymer is, for example, 5,000 or more and 30,000 or less.

For the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn), for example, a polystyrene conversion value obtained from a standard polystyrene (PS) calibration curve obtained by GPC measurement is used. The measurement conditions are, for example, 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 low molecular weight component amount in the first polymer is a component corresponding to a molecular weight of 1000 or less, which occupies the area of the entire molecular weight distribution based on, for example, data on molecular weight obtained by GPC measurement. It is calculated from the ratio of the total area.

The first polymer in the present embodiment contains, for example, an alkali metal. The concentration of the alkali metal in the first polymer (the mass of the alkali metal relative to the mass of the entire polymer) is preferably, for example, 10 ppm (mass ppm) or less.
By setting the alkali metal concentration in the first polymer within the range, the operation reliability of the electronic device including the permanent film can be improved. Moreover, if it is in the said range, it can accept | permit that an alkali metal is contained in a 1st polymer. That is, it becomes possible to perform the step of opening a ring anhydride in a structural unit derived from maleic anhydride, which will be described later, by treatment with an alkaline aqueous solution. In this case, the process can be performed in a short time and under mild conditions. Moreover, compared with the process of opening an anhydrous ring using an acid catalyst, control of the ring-opening rate in a 1st polymer becomes easy.
The lower limit of the alkali metal concentration in the first polymer is not particularly limited, but this embodiment allows the case where the alkali metal concentration in the first polymer is 0.01 ppm or more.

In the present embodiment, the alkali metal concentration in the first polymer is determined by measuring the alkali metal concentration relative to the solid content of the polymer diluted with N-methylpyrrolidone, if necessary, using a flameless atomic absorption photometer. Was obtained.
Moreover, as an alkali metal contained in the 1st polymer in this embodiment, Na, K, or Li is mentioned, for example. These alkali metals are caused by the aqueous alkali solution in the ring-opening step (treatment S2) for opening the anhydride ring in the maleic anhydride-derived structural unit described later, for example.

The alkali dissolution rate of the first polymer in the present embodiment is, for example, not less than 500 Å / second and not more than 20,000 秒 / second. The alkali dissolution rate of the first polymer is determined by, for example, applying a polymer solution prepared by dissolving the first polymer in propylene glycol monomethyl ether acetate and adjusting the solid content to 20% by weight on a silicon wafer by spin method. Calculated by impregnating a polymer film obtained by soft baking at 100 ° C. for 100 seconds with a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C. and visually measuring the time until the polymer film is erased. Is done.
By setting the alkali dissolution rate of the first polymer to 500 liters / second or more, the throughput in the development process using an alkali developer can be improved. Moreover, the residual film rate after the image development process by an alkali developing solution can be improved by making the alkali dissolution rate of the 1st polymer into 20,000 liters / second or less. For this reason, it is possible to suppress film loss due to the lithography process.

  The first polymer according to the present embodiment is produced as follows, for example.

(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 above formula (1).

Specific examples of the norbornene-type monomer represented by the formula (3) include bicyclo [2.2.1] -hept-2-ene (common name: norbornene), and further have an alkyl group. As those having an alkenyl group, such as 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, As those having an alkynyl group, such as 5-allyl-2-norbornene, 5- (2-propenyl) -2-norbornene, and 5- (1-methyl-4-pentenyl) -2-norbornene, 5-ethynyl-2 Examples of those having an aralkyl group such as norbornene include 5-benzyl-2-norbornene and 5-phenethyl-2-norbornene. And the like.
Any one or more of these can be used as the norbornene-type monomer. Especially, it is preferable to use bicyclo [2.2.1] -hept-2-ene (common name: norbornene) from a viewpoint of the light transmittance of a polymer.

Next, the norbornene type monomer represented by the formula (3) and maleic anhydride are subjected to addition polymerization. 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 (mole number of the compound represented by formula (3): mole number of maleic anhydride) is 0.5: 1 to 1: 0. .5 is preferable. Among these, from the viewpoint of controlling the molecular structure, it is preferable that the number of moles of the norbornene monomer represented by the formula (3): the number of moles of maleic anhydride = 1: 1.
The norbornene type monomer represented by the formula (3), the maleic anhydride, and the polymerization initiator are dissolved in a solvent, and then heated for a predetermined time, whereby the norbornene type monomer represented by the formula (3) and the maleic anhydride Solution polymerization is performed with an acid. The heating temperature is, for example, 50 to 80 ° C., and the heating time is 10 to 20 hours.

As the solvent, for example, any one or more of diethyl ether, tetrahydrofuran, toluene and the like can be used.
As the 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), 1,1′-azobis (cyclohexanecarbonitrile) (ABCN), Any one or more of these can be used.
Examples of organic peroxides include hydrogen peroxide, ditertiary butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP). Any one or more of them can be used.

  The amount (number of moles) of the polymerization initiator is preferably 1% to 10% of the total number of moles 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 5000-30000 by appropriately setting the amount of the polymerization initiator within the above range and appropriately setting the reaction temperature and reaction time.

By this polymerization step (treatment S1), the 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）において、ｎ、Ｒ_１〜Ｒ_４は、上記式（１）と同じである。すなわち、ｎは０、１，２のいずれかである。Ｒ_１〜Ｒ_４は、それぞれ独立した水素または炭素数１〜３０の有機基である。式（６）において、Ｒ_１〜Ｒ_４は、同一のものであっても異なっていてもよい）

(In the formula (6), n and R _{1 to} R ₄ are the same as those in the above formula (1). That is, n is either 0, 1, or 2. R _{1 to} R ₄ are each independent. Hydrogen or an organic group having 1 to 30 carbon atoms.In formula (6), R _{1 to} R ₄ may be the same or different.

  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. Moreover, the norbornene-type monomer shown by Formula (3) and maleic anhydride may be block copolymerized. 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 represented by the formula (6) A structure in which units are alternately arranged is preferable. That is, it is preferable that the copolymer 1 has the following repeating units.

（式（７）において、ｎ、Ｒ_１〜Ｒ_４は、上記式（１）と同じである。すなわち、ｎは０、１，２のいずれかである。Ｒ_１〜Ｒ_４は、水素または炭素数１〜３０の有機基である。Ｒ_１〜Ｒ_４は、同一のものであっても異なっていてもよい。また、ａは１０以上、２００以下の整数である）

(In the formula (7), n and R _{1 to} R ₄ are the same as those in the above formula (1). That is, n is 0, 1, or 2. R _{1 to} R ₄ are hydrogen or An organic group having 1 to 30 carbon atoms, R _{1 to} R ₄ may be the same or different, and a is an integer of 10 or more and 200 or less.

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 .

(Ring opening process (Process S2))
Next, among the repeating units of the cyclic structure derived from maleic anhydride of the obtained copolymer 1, the remaining repeating units are opened while some of the repeating units are closed. Thereby, the quantity of the carboxyl group in the copolymer 1 can be adjusted. That is, it is possible to control the acid value in the first polymer to be produced.
In this embodiment, among the repeating units derived from maleic anhydride of Copolymer 1, for example, 50% or more of the repeating units are not opened, and the cyclic structure (anhydrous ring) of the remaining repeating units is opened. It is preferable to do. The ring opening rate of the copolymer 1 is preferably less than 50%, for example. Among these, it is preferable that 60% or more and 90% or less of the repeating units of the cyclic structure derived from maleic anhydride of the copolymer 1 are not ring-opened.

Here, the ring-opening rate of the repeating unit derived from maleic anhydride can be measured as follows.
The IR absorption intensity (A1) of (C═O) in the acid anhydride structure of copolymer 1 before ring opening was measured, and the IR absorption intensity (A2) of (C═O) in the acid anhydride structure after ring opening (A2) ) To calculate the ring opening rate according to the following formula.
Ring-opening rate (%) = ((A1-A2) / A1) × 100
Acetonitrile is used as an internal standard substance.

In particular,
(A) Metal alkoxide as base (B) Alcohol or hydroxide of alkali metal as base is 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 stirred at 40 to 50 ° C. for 1 to 5 hours to obtain a reaction liquid L1. In the reaction liquid L1, a part of the anhydride ring of the repeating unit derived from the maleic anhydride of the copolymer 1 is opened, and a part of the terminal formed by the ring opening is esterified. The remaining terminals are not esterified and have a metal salt structure.

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

As the metal alkoxide described above, one represented by M (OR ₅ ) (M is a monovalent metal and R ₅ is an organic group having 1 to 18 carbon atoms) is preferable. Examples of the metal M include alkali metals, and sodium is preferable from the viewpoint of handleability. The R _5, are the same as those for _{R 5} in example above formula (2a) or Formula (2a).
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 maleic anhydride-derived structure of the copolymer 1 may be ring-opened in the presence of (B) an alcohol and an alkali metal hydroxide as a base.
As the alkali metal hydroxide, sodium hydroxide is preferable from the viewpoint of handleability.
As the alcohol, monovalent alcohol (R ₅ OH) is preferable. As R ₅ which is an organic group, those described above can be used. R ₅ preferably has 10 or less carbon atoms.

  The repeating unit derived from maleic anhydride opened in this ring-opening step (Process S2) has a structure represented by the following formula (8), and has a structure having a carboxyl group salt moiety. What has this structure of Formula (8) is called the copolymer 2.

（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 Formula (8), R ₅ is the same as R ₅ described above, and is derived from the alcohol or metal alkoxide described above).

  In addition, in the copolymer 2, although it is slight, the structure shown by following formula | equation (9) may be formed.

  Moreover, in the copolymer 2, although it is slight, the structure shown by following formula | equation (10) may be formed.

  Next, an aqueous solution such as hydrochloric acid or formic acid is added to the reaction solution L1, and the copolymer 2 is acid-treated to replace the metal ions (Na +) with protons (H +). Thereby, in the copolymer 3 obtained by acid-treating the copolymer 2, the ring-opened maleic anhydride-derived repeating unit represented by the formula (8) is represented by the following formula (11). It becomes a structure, and one terminal 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 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 acid-treating the copolymer 2 is represented by the above-described repeating unit represented by the formula (6), the repeating unit represented by the formula (5), and the formula (11). It has a repeating unit and, optionally, a structure of formula (9) and a structure of formula (12). Of the total number of structural units derived from maleic anhydride, 50% or more is the repeating unit represented by the formula (5). When the repeating unit represented by the formula (5) and the repeating unit represented by the formula (11) are included (the structure of the formula (9) and the structure of the formula (12) are represented by the formula (11) Ratio (molar ratio (formula (5): formula (11) (structure of formula (9), formula (9)) of the repeating unit, the structure of formula (9), and the structure of formula (12)) When the structure of 12) is included, the formula (11) + the formula (9) + the formula (12)))) is, for example, 1: 1 to 3: 1.

  Among these, it is preferable that the structure has the following formulas (13) and (14) as repeating units, and a structure derived from a norbornene monomer and a structure derived from a maleic anhydride monomer are alternately arranged. .

In Formula (13) and Formula (14), n and R _{1 to} R ₄ are the same as in Formula (1) above. That is, n is 0, 1, or 2. R _{1 to} R ₄ are hydrogen or an organic group having 1 to 30 carbon atoms. R _{1 to} R ₄ may be the same or different. In the structure of the formula (14), Z represents either one of —O—H and —O—R ₅ , and W is slightly different from the structure representing either one of Z and Any structure in which W is —O—R ₅ is included. R ₅ is the same as R ₅ described above.
In addition, although it is slight, the repeating unit represented by the formula (14) may include a structure in which both Z and W are —O—H.

In addition, 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.

  In this ring-opening step (treatment S2), 50% or more of the repeating units derived from maleic anhydride of copolymer 1 are not opened, and the cyclic structure (anhydrous ring) of the remaining repeating units is formed. Ring-opening yields copolymer 2. In the copolymer 2, as described above, a metal (for example, Na) is bonded to one end formed by opening an anhydrous maleic ring, but 50% or more of repeating units must not be opened. Thus, the amount of metal contained in the product polymer can be reduced. Thereby, the quantity of the alkali metal in the polymer finally obtained by this embodiment can be reduced, and the desired characteristic can be exhibited in the photosensitive resin composition using this polymer.

(Washing process (Processing S3))
Next, the solution containing the copolymer 3 obtained by the above steps is washed with a mixture of water and an organic solvent (for example, MEK) to remove residual metal components. Copolymer 3, residual monomers and oligomers move to the organic layer. Thereafter, the aqueous layer is removed (first cleaning).
Thereafter, again, a mixture of water and an organic solvent (for example, MEK) is added to the organic layer for washing (second washing).
In the present embodiment, the above-described cleaning step (processing S3) is repeated, for example, 5 times or more, more preferably 10 times. Thereby, the density | concentration of the alkali metal in the copolymer 3 can fully be reduced. In the present embodiment, it is preferable to repeat the washing step (treatment S3) so that the alkali metal concentration in the copolymer 3 is 10 ppm or less, preferably 5 ppm or less.

(Low molecular weight component removal step (processing S4))
Next, the organic layer containing the copolymer 3 and low molecular weight components such as residual monomers and oligomers is concentrated and then dissolved again in an organic solvent such as THF. And hexane and methanol are added to this solution, and the polymer containing the copolymer 3 is coagulated and precipitated. Here, as a low molecular weight component, a residual monomer, an oligomer, a polymerization initiator, and the like are included. Next, filtration is performed, and the obtained coagulum is dried. Thereby, the polymer which has the copolymer 3 from which the low molecular weight component was removed as a main component (main product) can be obtained.
In the present embodiment, in the low molecular weight component removing step (processing S4), it is preferable to repeat the extraction operation until the content of low nuclei having a molecular weight of 1000 or less in the copolymer 3 is 1% or less. Thereby, the amount of the low molecular weight component in the first polymer can be reduced to a degree sufficient to suppress the deformation of the film pattern during curing.

  In addition, when implementing the heating process mentioned later, in this low molecular weight component removal process (process S4), the said organic layer containing the copolymer 3, the residual monomer, and the oligomer is made into methanol, water, hexane, for example. Wash with mixture to remove organic layer.

(Heating step (Process S5))
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 (processing S2), an alkali developer (for example, TMAH (tetrahydroxide tetrahydroxide) of the first polymer is adjusted. Although the dissolution rate with respect to the aqueous methylammonium solution)) is adjusted, it is preferable to carry out this heating step (treatment S5) when it is necessary to strictly adjust the dissolution rate. In this heating step (Process S5), the dissolution rate of the first polymer in the alkaline developer is further adjusted by heating the copolymer 3.

A heating process (process S5) is performed as follows.
Alcohol is added to the liquid from which the organic layer has been removed in the low molecular weight component removing step to evaporate methanol, and then the mixture is heated at 120 to 140 ° C. for 0.5 to 10 hours. As the alcohol used here, any of those exemplified as the alcohol (R ₅ OH) described above can be used.

In this heating step (processing S5), a part of the carboxyl groups of the copolymer 3, that is, the carboxyl groups formed at the ends of the ring-opening structure of the structure derived from maleic anhydride are esterified. In addition to this, in this heating step (processing S5), the ring-opening 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 above formula (6), a repeating unit represented by the formula (5), a repeating unit represented by the formula (11), and the following: 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 (2b), 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 R ₅ described above, and the organic group having 1 to 18 carbon atoms of R ₆ is derived from the alcohol used in this heating step (processing S5). Including cases. In this case, R ₆ can be any of the organic groups exemplified for R ₅ described above.
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 group as R ₅ shown in the formula (9).
Furthermore, 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 all derived from the alcohol used in the main heating step (processing S5), and can be any of the organic groups exemplified for R ₅ described above.

Thereby, the product (polymer) which uses the copolymer 4 as a main product can be obtained.
Similarly to the copolymer 3, the copolymer 4 preferably has a structure in which a structure derived from a norbornene monomer and a structure derived from a maleic anhydride monomer are alternately arranged. And it is preferable that the copolymer 4 has a structure shown by Formula (16) in addition to Formula (13) and (14) mentioned above.

In the formula (16), n and R _{1 to} R ₄ are the same as those in the above formula (1). That is, n is 0, 1, or 2. R _{1 to} R ₄ are hydrogen or an organic group having 1 to 30 carbon atoms. R _{1 to} R ₄ may be the same or different. X represents one of —O—R ₆ and —O—R ₇ , and Y represents the other. R ₆ and R ₇ are the same as in the above formula (15).

  By passing through the above process, the 1st polymer which concerns on this embodiment shown in said Formula (1) will be obtained.

(Crosslinking agent)
(First cross-linking agent)
The first cross-linking agent is different from the above-mentioned second cross-linking agent that is an acrylic resin. This first cross-linking agent cross-links with the aforementioned polymer. For example, the first crosslinking agent preferably has a reactive group that reacts with a carboxyl group in the polymer to form a crosslinked structure. For example, a compound having a heterocycle as a reactive group is preferable. However, a compound having a glycidyl group or an oxetanyl group is preferable.
An example of the compound having a glycidyl group is an epoxy compound. This first cross-linking agent preferably has no acidic group.
Any of the following epoxy compounds can be used as the first crosslinking agent.
For example, bisphenol A epoxy resin (for example, LX-1, Daiso Chemical Co., Ltd.), 2,2 ′-((((1- (4- (2- (4- (oxiran-2-ylmethoxy) phenyl) propane- 2-yl) phenyl) ethane-1,1-diyl) bis (4,1-phenylene)) bis (oxy)) bis (methylene)) bis (oxirane) (for example, Techmore, VG3101L, Printec Co., Ltd.), Trimethylolpropane triglycidyl ether (eg, TMPTGE, CVC Specialty Chemicals), and 1,1,3,3,5,5-hexamethyl-1,5-bis (3- (oxiran-2-ylmethoxy) Propyl) trisiloxane (for example, DMS-E09, Gerest). These structures are shown below. Other examples include Araldite MT0163 and Araldite CY179 (Ciba Geigy), EHPE-3150, and Epolite GT300 (Daicel Chemical Industries, Ltd.). Any one or more of the above can be used. In addition, it is not limited to the illustration here.

ここで、ｎ１の平均値は、０以上３以下の正数である。

Here, the average value of n1 is a positive number of 0 or more and 3 or less.

  Moreover, as an epoxy resin, it is preferable to use a polyfunctional alicyclic epoxy resin from the viewpoint of the transparency of a photosensitive resin composition, and a dielectric constant. As a polyfunctional alicyclic epoxy resin, what is shown by the following chemical formula can be used, for example. This epoxy resin is, for example, Poly [(2-oxylanyl) -1,2-cyclohexanediol] 2-ethyl-2- (hydroxymethyl) -1,3-propandiol ether (3: 1).

式中、Ｒ^３６は炭素数１〜１０の炭化水素基、ｓは１〜３０の整数、ｔは１〜６の整数である。

In the formula, R ³⁶ is a hydrocarbon group having 1 to 10 carbon atoms, s is an integer of 1 to 30, and t is an integer of 1 to 6.

Moreover, as a compound which has an oxetanyl group, any of the following can be used, for example.
For example, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, bis [1-ethyl (3-oxetanyl)] methyl ether, 4,4′-bis [(3-ethyl-3- Oxetanyl) methoxymethyl] biphenyl, 4,4′-bis (3-ethyl-3-oxetanylmethoxy) biphenyl, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, diethylene glycol bis (3-ethyl-3-oxetanyl) Methyl) ether, bis (3-ethyl-3-oxetanylmethyl) diphenoate, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, poly [ [3-[(3-Ethyl-3-oxy Taniru) methoxy] propyl] silasesquioxane] derivatives, oxetanyl silicate, phenol novolak type oxetane, 1,3-bis [(3-ethyl oxetane over 3-yl) methoxy] Although benzene, and the like, without limitation. These may be used alone or in combination.

(Second crosslinking agent)
The second crosslinking agent is an acrylic resin that reacts with at least one of the polymer and the first crosslinking agent to form a crosslinked structure.
For example, when the polymer described above has a carboxyl group, the second crosslinking agent preferably has a reactive group that reacts with the carboxyl group to form a crosslinked structure. As the second crosslinking agent, for example, a compound having a hetero ring as a reactive group is preferable, and an acrylic resin having a glycidyl group or an oxetanyl group is particularly preferable. Moreover, when the polymer mentioned above has a carboxyl group, the 2nd crosslinking agent may be an acrylic resin which has OH group as a reactive group which reacts with this carboxyl group and forms a crosslinked structure.
In addition, when the first cross-linking agent described above has a cyclic ether group, it preferably has a reactive group that reacts with the cyclic ether group to form a cross-linked structure. For example, an acrylic resin having a carboxyl group as a reactive group is preferable.
Furthermore, the second cross-linking agent may be one that cross-links to both the polymer and the first cross-linking agent, for example, an acrylic resin having both a cyclic ether group and a carboxyl group. Good.
Moreover, the acrylic resin may include a cyclic hydrocarbon structure. By including such a structure, the dielectric constant of the film composed of the photosensitive resin composition can be lowered.
For example, the following can be illustrated as an acrylic resin.

なお、式（I）で示されるアクリル樹脂、式（II）で示されるアクリル樹脂、式（III）で示されるアクリル樹脂は、いずれもブロック共重合体であってもよく、ランダム共重合体であってもよい。
式（I）において、ａ〜ｄは、アクリル樹脂中のモル含有率を示し、ａ＋ｂ＋ｃ＋ｄ＝１である。また、０．３≦ａ≦０．４、０．３５≦ｂ≦０．４５、０．０５≦ｃ≦０．１５、０．１≦ｄ≦０．２である。
式（II）において、ｅ〜ｈは、アクリル樹脂中のモル含有率を示し、ｅ＋ｆ＋ｇ＋ｈ＝１である。また、０．２５≦ｅ≦０．３５、０．１５≦ｆ≦０．３、０．２５≦ｇ≦０．３５、０．１≦ｈ≦０．３である。
式（III）において、ｉ〜ｋは、アクリル樹脂中のモル含有率を示し、ｉ＋ｊ＋ｋ＝１である。また、０．１≦ｉ≦０．３、０．３５≦ｊ≦０．５５、０．２≦ｋ≦０．４である。
さらには、アクリル樹脂として、綜研化学社製のＺＡＨ−３０６（酸価６１−６７ｍｇＫＯＨ／ｇ）、ＺＡＨ−３１０（酸価９３−９９ｍｇＫＯＨ／ｇ）、ＺＡＨ−３１５（酸価１４７−１５３ｍｇＫＯＨ／ｇ）、ＺＡＨ−１０６（酸価５８−６６ｍｇＫＯＨ／ｇ）、ＺＡＨ−１１０（酸価９３−９９ｍｇＫＯＨ／ｇ）、ＺＡＨ−１１５（酸価１４０−１５５ｍｇＫＯＨ／ｇ）を使用することができる。
また、綜研化学社製のＣＢ−３０９８（酸価９５．８ｍｇＫＯＨ／ｇ）、ＣＢＢ−３０９８（酸価９８ｍｇＫＯＨ／ｇ）を使用することができる。
アクリル樹脂としては、例示したもののうち、少なくともいずれか１種以上を使用することが好ましい。なお、これらはいずれもカルボキシル基を含むアクリル樹脂である。

The acrylic resin represented by formula (I), the acrylic resin represented by formula (II), and the acrylic resin represented by formula (III) may all be block copolymers or random copolymers. There may be.
In the formula (I), a to d indicate the molar content in the acrylic resin, and a + b + c + d = 1. Further, 0.3 ≦ a ≦ 0.4, 0.35 ≦ b ≦ 0.45, 0.05 ≦ c ≦ 0.15, and 0.1 ≦ d ≦ 0.2.
In the formula (II), e to h represent molar contents in the acrylic resin, and e + f + g + h = 1. Also, 0.25 ≦ e ≦ 0.35, 0.15 ≦ f ≦ 0.3, 0.25 ≦ g ≦ 0.35, and 0.1 ≦ h ≦ 0.3.
In the formula (III), i to k represent the molar content in the acrylic resin, and i + j + k = 1. Further, 0.1 ≦ i ≦ 0.3, 0.35 ≦ j ≦ 0.55, and 0.2 ≦ k ≦ 0.4.
Furthermore, as acrylic resins, ZAH-306 (acid value 61-67 mgKOH / g), ZAH-310 (acid value 93-99 mgKOH / g), ZAH-315 (acid value 147-153 mgKOH / g) manufactured by Soken Chemical Co., Ltd. ZAH-106 (acid value 58-66 mgKOH / g), ZAH-110 (acid value 93-99 mgKOH / g), ZAH-115 (acid value 140-155 mgKOH / g) can be used.
Further, CB-3098 (acid value 95.8 mgKOH / g) and CBB-3098 (acid value 98 mgKOH / g) manufactured by Soken Chemical Co., Ltd. can be used.
As the acrylic resin, it is preferable to use at least one of the exemplified ones. These are all acrylic resins containing a carboxyl group.

Here, it is preferable that the acrylic resin has a carboxyl group. By using such an acrylic resin, solubility in an alkaline developer can be ensured even when the amount of the crosslinking agent is increased. Thereby, developability becomes favorable and a desired pattern can be formed.
Further, by using an acrylic resin as the second crosslinking agent, an acrylic skeleton can be introduced into the cured film of the photosensitive resin composition, and the light transmittance of the cured film composed of the photosensitive resin composition Can be secured.
Furthermore, since an acrylic skeleton can be introduced into the cured film of the photosensitive resin composition by using an acrylic resin as the second crosslinking agent, the cured film composed of the photosensitive resin composition is flexible. Property, and the occurrence of cracks in the cured film can be suppressed.

(Photosensitive agent)
When the photosensitive resin composition is a positive type, a photoactive compound can be used as the photosensitive agent, for example, a diazoquinone compound can be used.
For example, any one or more of the following can be used.

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 one of the structures shown below or a hydrogen atom. However, at least one of Q of each compound is any of the following.
Of these, an o-naphthoquinone diazide sulfonic acid derivative in which Q is (a) or (b) is preferable from the viewpoint of transparency and dielectric constant of the photosensitive resin composition.

なお、ポジ型の感光性樹脂組成物には、上述した光活性化合物に加えて、光あるいは熱で酸を発生する酸発生剤が含まれていてもよい。このような酸発生剤を含むことで、感光性樹脂組成物を露光現像した後、光を照射あるいは加熱することで、架橋剤の架橋反応を促進させることができる。
この場合には、酸発生剤は、架橋剤１００質量部に対して、３質量部以下であることが好ましい。
光により酸を発生する光酸発生剤としては、後述するものを使用できる。
熱により酸を発生する熱酸発生剤としては、ＳＩ−４５Ｌ，ＳＩ−６０Ｌ，ＳＩ−８０Ｌ，ＳＩ−１００Ｌ，ＳＩ−１１０Ｌ，ＳＩ−１５０Ｌ（三新化学工業（株）製）等の芳香族スルホニウム塩が使用できる。
熱酸発生剤の含有量は、たとえば、樹脂組成物の全固形分を１００質量％としたとき、０．１〜５質量％であることが好ましい。

In addition to the photoactive compound described above, the positive photosensitive resin composition may contain an acid generator that generates an acid by light or heat. By including such an acid generator, the crosslinking reaction of the crosslinking agent can be promoted by irradiating or heating the photosensitive resin composition after exposure and development.
In this case, the acid generator is preferably 3 parts by mass or less with respect to 100 parts by mass of the crosslinking agent.
As the photoacid generator that generates an acid by light, those described later can be used.
As thermal acid generators that generate acid by heat, aromatics such as SI-45L, SI-60L, SI-80L, SI-100L, SI-110L, SI-150L (manufactured by Sanshin Chemical Industry Co., Ltd.) A sulfonium salt can be used.
The content of the thermal acid generator is preferably 0.1 to 5% by mass, for example, when the total solid content of the resin composition is 100% by mass.

  Further, when the photosensitive resin composition is a negative type, a photoacid generator can be used as the photosensitive agent. Any photoacid generator may be used as long as it absorbs light energy to generate Bronsted acid or Lewis acid. For example, triphenylsulfonium trifluoromethanesulfonate, tris (4-t-butylphenyl) sulfonium- Sulfonium salts such as trifluoromethanesulfonate, diazonium salts such as p-nitrophenyldiazonium hexafluorophosphate, ammonium salts, phosphonium salts, diphenyliodonium trifluoromethanesulfonate, iodonium salts such as (triccumyl) iodonium-tetrakis (pentafluorophenyl) borate, Quinonediazides, diazomethanes such as bis (phenylsulfonyl) diazomethane, 1-phenyl-1- (4-methylphenyl) sulfonyl Sulfonic acid esters such as xyl-1-benzoylmethane and N-hydroxynaphthalimide-trifluoromethanesulfonate, disulfones such as diphenyldisulfone, tris (2,4,6-trichloromethyl) -s-triazine, 2- ( And compounds such as triazines such as 3,4-methylenedioxyphenyl) -4,6-bis- (trichloromethyl) -s-triazine. These photoacid generators can be used alone or in combination.

In the above photosensitive resin composition, when the photosensitive resin composition is a positive type, the ratio of each component is as follows, for example.
When the total solid content (that is, the component excluding the solvent) of the resin composition is 100% by mass, the first polymer described above is preferably contained in an amount of 30% by mass to 70% by mass, and in particular, 35% by mass. It is preferable to contain -50 mass%.
Moreover, when the total solid content (namely, component except a solvent) of a resin composition is 100 mass%, it is preferable to contain 15 mass%-40 mass% of 1st crosslinking agents, Especially, 20 mass% It is preferable to contain -35 mass%.
Further, when the total solid content of the resin composition (that is, the component excluding the solvent) is 100% by mass, the second crosslinking agent is preferably contained in an amount of 5% by mass to 30% by mass, and in particular, 8% by mass. It is preferable to contain -26 mass%.
Furthermore, when the total solid content of the resin composition (that is, the component excluding the solvent) is 100% by mass, the photoactive compound as the photosensitizer is preferably 5 to 20% by mass. More preferably, it is 10-15 mass%.

Moreover, when the photosensitive resin composition is a negative type, the ratio of each component is as follows, for example.
When the total solid content (that is, the component excluding the solvent) of the resin composition is 100% by mass, the first polymer described above is preferably contained in an amount of 30% by mass to 70% by mass, and in particular, 35% by mass. It is preferable to contain -50 mass%.
Moreover, when the total solid content (namely, component except a solvent) of a resin composition is 100 mass%, it is preferable to contain 15 mass%-40 mass% of 1st crosslinking agents, Especially, 20 mass% It is preferable to contain -35 mass%.
Further, when the total solid content of the resin composition (that is, the component excluding the solvent) is 100% by mass, the second crosslinking agent is preferably contained in an amount of 5% by mass to 30% by mass, and in particular, 8% by mass. It is preferable to contain -26 mass%.
Furthermore, when the total solid content of the resin composition (that is, the component excluding the solvent) is 100% by mass, the amount of the photoacid generator is preferably 0.1 to 40% by mass, and a high resolution pattern From the point which can form a film | membrane, More preferably, it is 1-30 mass%.

Moreover, you may add additives, such as antioxidant, a filler, surfactant, and a sensitizer, in the photosensitive resin composition mentioned above as needed.
As the antioxidant, one or more selected from the group of phenolic antioxidants, phosphorus antioxidants, and thioether antioxidants can be used. Antioxidants can suppress oxidation during curing and oxidation of the film in subsequent processes.
Examples of phenolic antioxidants include pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3-t -Butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} 2,4,8,10-tetraoxaspiro [5,5] undecane, octadecyl-3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl -2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 2,6-di-t-butyl-4-methylphenol, 2,6-di- -Butyl-4-ethylphenol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-t-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-t -Butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-t-butyl-m-cresol) 2-octylthio-4,6-di (3,5-di-t-butyl-4-hydroxyphenoxy) -s-triazine, 2,2′-methylenebis (4-methyl-6-t-butyl-6- Butylphenol), 2, -2'-methylenebis (4-ethyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3- -Butylphenyl) butyric acid] glycol ester, 4,4'-butylidenebis (6-t-butyl-m-cresol), 2,2'-ethylidenebis (4,6-di-t-butylphenol), 2, 2′-ethylidenebis (4-s-butyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-t- Butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-t- Butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3 , 5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 2-t -Butyl-4-methyl-6- (2-acryloyloxy-3-t-butyl-5-methylbenzyl) phenol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4- 8,10-tetraoxaspiro [5,5] undecane-bis [β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], triethylene glycol bis [β- (3-t-butyl -4-hydroxy-5-methylphenyl) propionate], 1,1'-bis (4-hydroxyphenyl) cyclohexane, 2,2'-methylene (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,2'-methylenebis (6- (1-methylcyclohexyl) -4-methylphenol) 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis (2- (3-tert-butyl-4-hydroxy-5-methylphenylpropionyloxy) 1,1-dimethylethyl) 2,4,8,10-tetraoxaspiro (5,5) undecane, 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4'-bis (3,5-di-t-) Butyl-4-hydroxybenzyl) sulfide, 4,4′-thiobis (6-tert-butyl-2-methylphenol), 2,5-di-tert-butylhydroquinone, 2,5-di t-amylhydroquinone, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-dimethyl-6- (1-methylcyclohexyl) styreneated Phenol, 2,4-bis ((octylthio) methyl) -5-methylphenol, and the like. In these, a hindered phenolic antioxidant is preferable.
Phosphorus antioxidants include bis- (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, tris (2,4-di-t-butylphenylphosphite), tetrakis ( 2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, bis- (2,6- Dicumylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, tris (mixed mono and di-nonylphenyl phosphite), bis (2,4 -Di-t-butylphenyl) pentaerythritol-di-phosphite, bis (2,6-di-t-butyl-4-methoxy) Cicarbonylethyl-phenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-octadecyloxycarbonylethyl-phenyl) pentaerythritol diphosphite, and the like. Of these, phosphites and phosphates are preferred.
Examples of the thioether-based antioxidant include dilauryl 3,3′-thiodipropionate, bis (2-methyl-4- (3-n-dodecyl) thiopropionyloxy) -5-t-butylphenyl) sulfide, distearyl- 3,3′-thiodipropionate, pentaerythritol-tetrakis (3-lauryl) thiopropionate and the like can be mentioned.
Antioxidant can be 0.1-5 mass% of the whole photosensitive resin composition.
The above photosensitive resin composition 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, or mixtures thereof can be employed. In addition, it is not limited to what was illustrated here.

The physical properties of the photosensitive resin composition as described above are preferably as follows.
(1) Relative dielectric constant The photosensitive resin composition was applied, exposed to ultraviolet rays at 300 mJ / cm ² , then heated at 230 ° C. for 60 minutes to form a film having a thickness of 2 μm, and then measured at a frequency of 10 kHz. The relative dielectric constant is 4.0 or less. Especially, it is preferable that it is 3.5 or less. The lower limit value of the relative dielectric constant is not particularly limited, but is, for example, 1.
More specifically, the relative dielectric constant can be measured as follows.
The photosensitive resin composition is spin-coated on an aluminum substrate and baked on a hot plate at 100 ° C. for 120 seconds. Then, ultraviolet rays are exposed at 300 mJ / cm ² and post-baked by heating at 230 ° C. for 60 minutes in an oven to form a film having a thickness of 2 μm.
Thereafter, a gold electrode is formed on the film and measured under conditions at room temperature (25 ° C.) and 10 kHz.

(2) Transmittance Further, after the photosensitive resin composition was applied and exposed at 300 mJ / cm ² , the film was heated at 230 ° C. for 60 minutes to form a film having a thickness of 2 μm. The transmittance of light at 400 nm is 80% or more. Especially, it is preferable that the said transmittance | permeability is 85% or more. The upper limit of the transmittance is not particularly limited, but is 99%, for example.
The transmittance can be measured as follows.
The photosensitive resin composition is spin-coated on a glass substrate (rotation number: 500 to 2500 rpm) and baked on a hot plate at 100 ° C. for 120 seconds. Thereafter, after exposure at 300 mJ / cm ² , post baking is performed by heating in an oven at 230 ° C. for 60 minutes to form a film having a thickness of 2 μm.
The transmittance of the film at a wavelength of 400 nm is measured using an ultraviolet-visible light spectrophotometer.
As described above, a film composed of the photosensitive resin composition has a low relative dielectric constant. Thereby, the photosensitive resin composition can be used for a semiconductor device or the like. Furthermore, a film composed of the photosensitive resin composition has a high light transmittance. Although described later in detail, for example, the photosensitive resin composition can be applied to an optoelectronic device.

(3) Residual film ratio The residual film ratio of the above photosensitive resin composition can be measured as follows.
The photosensitive resin composition is spin-coated on a silicon wafer, and heated on a hot plate at 100 ° C. for 120 seconds to form a thin film A. The thin film B is obtained by exposing with an exposure apparatus so that the width of a 10 μm line and the space becomes 1: 1 and developing with a 0.4 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 90 seconds.
Then, after ultraviolet exposure at 300 mJ / cm ² , post baking is performed by heating in an oven at 230 ° C. for 60 minutes.
From the film thicknesses of the thin film A, the thin film B, and the thin film C obtained by the above method, the remaining film ratio was calculated from the following formula.
Residual film ratio after development (%) = [film thickness of thin film B (μm) / film thickness of thin film A (μm)] × 100
Residual film ratio after baking (%) = [film thickness of thin film C (μm) / film thickness of thin film A (μm)] × 100
The photosensitive resin composition preferably has a residual film ratio after development of 90% or more. Moreover, it is preferable that the film ratio after baking is 80% or more.

(4) Solvent resistance The layer formed by spin coating and baked on a hot plate at 100 ° C. for 136 seconds is 90% in developer (0.5 wt% tetramethylammonium hydroxide aqueous solution (TMAH)). Soak in seconds and rinse with pure water. Next, ultraviolet light is exposed at 300 mJ / cm ² , and then heated in an oven at 230 ° C. for 60 minutes, the first film thickness is defined as the first film thickness, and the first film is N-methylpyrrolidone. When the film thickness after immersion at 70 ° C. for 15 minutes is the second film thickness, [{(second film thickness) − (first film thickness)} / (first film thickness)] × Satisfies 100 ≦ 5 (%).

  According to the photosensitive resin composition of the present embodiment having such characteristics, the film thickness hardly changes even when immersed in N-methylpyrrolidone in the manufacturing process after film formation. For this reason, it becomes possible to manufacture a film having a predetermined design thickness with high accuracy.

(Electronic device)
Next, the structure of the electronic device 100 using the above photosensitive resin composition is demonstrated.
1 and 2 are cross-sectional views showing examples of the electronic device 100 according to the present embodiment. In any case, a part of the electronic device 100 including the insulating film 20 is shown.
The electronic device 100 according to the present embodiment includes an insulating film 20 that is a permanent film formed of the photosensitive resin composition containing the first polymer, for example.

  As an example of the electronic apparatus 100 according to the present embodiment, a liquid crystal display device is shown in FIG. However, the electronic device 100 according to this embodiment is not limited to a liquid crystal display device, and includes other electronic devices including a permanent film made of a photosensitive resin composition.

  As shown in FIG. 1, an electronic device 100 that is a liquid crystal display device includes, for example, a substrate 10, a transistor 30 provided on the substrate 10, and an insulating film 20 provided on the substrate 10 so as to cover the transistor 30. And a wiring 40 provided on the insulating film 20.

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 according to the present embodiment 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 said 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 is 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. Thus, a planarization film that covers the transistor 30 provided over the substrate 10 is formed.
Next, the insulating film 20 is exposed to ultraviolet light or the like and developed to form an opening 22 in a part of the insulating film 20. When the photosensitive resin composition is a positive type, the exposed portion is dissolved in the developer, and the unexposed portion remains. On the other hand, when the photosensitive resin composition is a negative type, the unexposed portion is dissolved in the developer and the exposed portion remains. This also applies to each example of the electronic device 100 described later.
Next, the insulating film 20 is heated and cured. Then, 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.

As an example of the electronic device 100 according to the present embodiment, FIG. 2 shows a semiconductor device in which the insulating films 52 and 54 are formed of a permanent film made of the photosensitive resin composition.
An electronic device 100 shown in FIG. 2 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). An insulating film 50 that is an interlayer insulating film and an uppermost layer wiring 72 provided on the insulating film 50 are provided in the uppermost layer of the multilayer wiring layer. The uppermost layer wiring 72 is made of, for example, Al.

A layer 80 is provided on the insulating film 50. The layer 80 includes an insulating film 52 provided on the insulating film 50 so as to cover the uppermost layer wiring 72, a rewiring layer 70 provided on the insulating film 52, and on the insulating film 52 and the rewiring layer 70. And an insulating film 54 provided.
An opening 24 connected to the uppermost layer wiring 72 is formed in the insulating film 52. The rewiring layer 70 is formed on the insulating film 52 and in the opening 24, and is connected to the uppermost layer wiring 72. An opening 26 connected to the rewiring layer 70 is provided in the insulating film 54.
The insulating film 52 and the insulating film 54 are composed of permanent films made of the photosensitive resin composition. The insulating film 52 can be obtained, for example, by exposing the photosensitive resin composition applied on the insulating film 50 to ultraviolet rays and developing it to form the opening 24 and then heat-curing it. The insulating film 54 is obtained, for example, by exposing the photosensitive resin composition applied on the insulating film 52 to ultraviolet rays, developing the openings 26 by performing development, and then heat-curing the openings 26. .

  For example, bumps 74 are formed in the openings 26. The electronic device 100 is connected to a wiring board or the like via bumps 74, for example.

  Furthermore, the electronic device 100 according to the present embodiment may be an optical device in which a microlens is configured by a permanent film made of the photosensitive resin composition. Examples of the optical device include a liquid crystal display device, a plasma display, a field emission display, and an electroluminescence display.

  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.
<Synthesis Example 1>
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 mass 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%. As a result, 1107.7 g of a 20 wt% polymer solution was obtained (GPC Mw = 13,700, Mn = 7,400). The obtained polymer is a copolymer of the formula (1), and includes a structural unit represented by the formula (2a) and a structural unit represented by the formula (2c).

<Example 1>
485.2 g of a 20.6% PGMEA solution of the resin (A1) described in Synthesis Example 1 and an esterified product of a compound represented by the following formula B1 and 1,2-naphthoquinonediazide-5-sulfonyl chloride (Daitokemix Co., Ltd.) 30 g of PA-28), 26 g of epoxy resin EHPE-3150 (manufactured by Daicel Chemical Industries), 5 g of epoxy resin VG3101L (manufactured by Printec), 15 g of epoxy resin Epolite 100MF (manufactured by Kyoeisha), acrylic resin (Soken Chemical Co., Ltd.) CB-3098) 20.2 g, 10 g of KBM-303 (manufactured by Shin-Etsu Silicone) to improve the adhesion between the photosensitive resin composition and the substrate, on the film when the photosensitive resin composition is spin-coated In order to prevent radial striations that can be made, 0.5 g of F-557 (manufactured by DIC) After dissolving in ethylene glycol methyl ethyl ether (DEGMEE) and stirring, it was filtered through a 0.2 μm filter to prepare a photosensitive resin composition.

The following evaluation was performed on Example 1 and Examples and Comparative Examples described later.
(Evaluation of relative dielectric constant)
A 2.0 μm thick thin film without pattern was obtained on an aluminum substrate.
Specifically, the photosensitive resin composition described above was spin-coated on an HMDS (hexamethyldisilazane) -treated aluminum substrate (rotation number: 500 to 2500 rpm), baked on a hot plate at 100 ° C. for 120 seconds, and about A thin film having a thickness of 2.5 μm was obtained.
This thin film is exposed on the entire surface of g + h + i line with Canon g + h + i line mask aligner PLA-501F (extra-high pressure mercury lamp) so that the integrated light quantity becomes 300 mJ / cm ^2, and then heated in an oven at 230 ° C. for 60 minutes. Thus, a post-bake treatment was performed to obtain a thin film having a thickness of 2 μm. Thereafter, a gold electrode was formed on this thin film, and the relative dielectric constant was calculated from the capacitance obtained using a Hewlett Packard LCR meter (4282A) under the conditions of room temperature (25 ° C.) and 10 kHz.

(Evaluation of transmittance)
Using a 1737 glass substrate manufactured by Corning Inc. having a size of 100 mm in length and 100 mm in width, a thin film having no pattern was obtained on the glass substrate by performing the same operation as above except that the test pattern was not exposed and developed.
Specifically, the photosensitive resin composition described above was spin-coated on a glass substrate treated with HMDS (hexamethyldisilazane) (rotation number: 500-2500 rpm), baked on a hot plate at 100 ° C. for 120 seconds, and about A thin film having a thickness of 2.5 μm was obtained.
This thin film was exposed to 300 mJ / cm ^{2 of} g + h + i line with PLA-501F and then post-baked by heating in an oven at 230 ° C. for 60 minutes to obtain a thin film having a thickness of 2 μm. For this thin film, the transmittance (%) of light at a wavelength of 400 nm was measured using an ultraviolet-visible light spectrophotometer.

(Evaluation of solvent resistance)
The same operation as the evaluation of the transmittance was performed to obtain a glass substrate with a thin film.
Specifically, the photosensitive resin composition described above was spin-coated on a glass substrate treated with HMDS (hexamethyldisilazane) (rotation number: 500-2500 rpm), baked on a hot plate at 100 ° C. for 120 seconds, and about A thin film having a thickness of 2.5 μm was obtained.
Thereafter, it was immersed in a developer (0.5 wt% TMAH) for 90 seconds and rinsed with pure water. Thereafter, this thin film was exposed to 300 mJ / cm ^{2 of} g + h + i line with PLA-501F, and then heated in an oven at 230 ° C. for 60 minutes. Next, it was immersed in N-methylpyrrolidone (Kanto Chemical, purity 99% or more) at 70 ° C. for 15 minutes, rinsed with pure water for 30 seconds, and then spin-dried under the condition of 2000 rpm. The swelling ratio was calculated by (film thickness after solvent immersion / film thickness after solvent immersion) × 100.
Moreover, after being immersed in 70 degreeC N-methylpyrrolidone (Kanto Chemical) for 15 minutes, the film | membrane which performed the pure water rinse was heated in 230 degreeC for 15 minutes, and the film thickness was measured. The recovery rate is a value calculated by (film thickness after heating after solvent immersion / film thickness before solvent immersion) × 100, and a high recovery rate indicates that the film is not dissolved by the solvent. .

<Example 2>
485.2 g of a 20.6% PGMEA solution of the resin (A1) described in Synthesis Example 1 and an esterified product of the compound represented by the formula B1 and 1,2-naphthoquinonediazide-5-sulfonyl chloride (Daitokemix Co., Ltd.) 30 g of PA-28), 26 g of epoxy resin EHPE-3150 (manufactured by Daicel Chemical Industries), 5 g of epoxy resin VG3101L (manufactured by Printec), 15 g of epoxy resin Epolite 100MF (manufactured by Kyoeisha), acrylic resin (Soken Chemical Co., Ltd.) CBB-3098) 20.2 g, 10 g of KBM-303 (manufactured by Shin-Etsu Silicone) to improve the adhesion between the photosensitive resin composition and the substrate, on the film when spin coating the photosensitive resin composition In order to prevent radial striation that can be made, 0.5 g of F-557 (manufactured by DIC) After dissolving in diethylene glycol methyl ethyl ether (DEGMEE) and stirring, it was filtered through a 0.2 μm filter to prepare a photosensitive resin composition.

<Example 3>
485.2 g of a 20.6% PGMEA solution of the resin (A1) described in Synthesis Example 1 and an esterified product of the compound represented by the formula B1 and 1,2-naphthoquinonediazide-5-sulfonyl chloride (Daitokemix Co., Ltd.) 30 g of PA-28), 26 g of epoxy resin EHPE-3150 (manufactured by Daicel Chemical Industries), 5 g of epoxy resin VG3101L (manufactured by Printec), 15 g of epoxy resin Epolite 100MF (manufactured by Kyoeisha), acrylic resin (Soken Chemical Co., Ltd.) ZAH-110) 56.7 g, 10 g of KBM-303 (manufactured by Shin-Etsu Silicone) to improve the adhesion between the photosensitive resin composition and the substrate, and on the film when the photosensitive resin composition is spin-coated. In order to prevent radial striations that can be made, 0.5 g of F-557 (manufactured by DIC) After dissolving in ethylene glycol methyl ethyl ether (DEGMEE) and stirring, it was filtered through a 0.2 μm filter to prepare a photosensitive resin composition.

<Example 4>
485.2 g of a 20.6% PGMEA solution of the resin (A1) described in Synthesis Example 1 and an esterified product of the compound represented by the formula B1 and 1,2-naphthoquinonediazide-5-sulfonyl chloride (Daitokemix Co., Ltd.) 30 g of PA-28), 26 g of epoxy resin EHPE-3150 (manufactured by Daicel Chemical Industries), 5 g of epoxy resin VG3101L (manufactured by Printec), 15 g of epoxy resin Epolite 100MF (manufactured by Kyoeisha), acrylic resin (Soken Chemical Co., Ltd.) ZAH-310) 56.5 g, 10 g of KBM-303 (manufactured by Shin-Etsu Silicone) to improve the adhesion between the photosensitive resin composition and the substrate, and on the film when the photosensitive resin composition is spin-coated In order to prevent radial striations that can be made, 0.5 g of F-557 (manufactured by DIC) After dissolving in ethylene glycol methyl ethyl ether (DEGMEE) and stirring, it was filtered through a 0.2 μm filter to prepare a photosensitive resin composition.

<Example 5>
485.2 g of a 20.6% PGMEA solution of the resin (A1) described in Synthesis Example 1 and an esterified product of the compound represented by the formula B1 and 1,2-naphthoquinonediazide-5-sulfonyl chloride (Daitokemix Co., Ltd.) 30 g of manufactured PA-28), 26 g of epoxy resin EHPE-3150 (manufactured by Daicel Chemical Industries), 5 g of epoxy resin VG3101L (manufactured by Printec Co., Ltd.), 15 g of epoxy resin Epolite100MF (manufactured by Kyoeisha), represented by formula (I) 62.9 g of an acrylic resin (manufactured by Daitokemix, in formula (I), a = 0.35, b = 0.4, c = 0.1, d = 0.15), the photosensitive resin composition and the substrate In order to improve adhesion, 10 g of KBM-303 (manufactured by Shin-Etsu Silicone Co., Ltd.) was released on the film when the photosensitive resin composition was spin-coated. In order to prevent ray-like striations, 0.5 g of F-557 (manufactured by DIC) was dissolved in an appropriate amount of diethylene glycol methyl ethyl ether (DEGMEE), stirred, and then filtered through a 0.2 μm filter. A resin composition was prepared.

<Example 6>
485.2 g of a 20.6% PGMEA solution of the resin (A1) described in Synthesis Example 1 and an esterified product of the compound represented by the formula B1 and 1,2-naphthoquinonediazide-5-sulfonyl chloride (Daitokemix Co., Ltd.) 30 g of PA-28), 26 g of epoxy resin EHPE-3150 (manufactured by Daicel Chemical Industries), 5 g of epoxy resin VG3101L (manufactured by Printec), 15 g of epoxy resin Epolite 100MF (manufactured by Kyoeisha), represented by the formula (II) 62.9 g of an acrylic resin (manufactured by Daitokemix, e = 0.28, f = 0.22, g = 0.3, h = 0.2 in the formula (II)), In order to improve adhesion, 10 g of KBM-303 (manufactured by Shin-Etsu Silicone Co., Ltd.) was released on the film when the photosensitive resin composition was spin-coated. In order to prevent ray-like striations, 0.5 g of F-557 (manufactured by DIC) was dissolved in an appropriate amount of diethylene glycol methyl ethyl ether (DEGMEE), stirred, and then filtered through a 0.2 μm filter. A resin composition was prepared.

<Example 7>
485.2 g of a 20.6% PGMEA solution of the resin (A1) described in Synthesis Example 1 and an esterified product of the compound represented by the formula B1 and 1,2-naphthoquinonediazide-5-sulfonyl chloride (Daitokemix Co., Ltd.) 30 g of PA-28), 26 g of epoxy resin EHPE-3150 (manufactured by Daicel Chemical Industries), 5 g of epoxy resin VG3101L (manufactured by Printec), 15 g of epoxy resin Epolite 100MF (manufactured by Kyoeisha), represented by formula (III) 63.5 g of acrylic resin (manufactured by Daitokemix Co., Ltd., i = 0.22, j = 0.48, k = 0.3 in formula (III)), in order to improve the adhesion between the photosensitive resin composition and the substrate 10 g of KBM-303 (manufactured by Shin-Etsu Silicone Co., Ltd.), a radial stain formed on the film when the photosensitive resin composition is spin-coated. In order to prevent the relation, 0.5 g of F-557 (manufactured by DIC) was dissolved in an appropriate amount of diethylene glycol methyl ethyl ether (DEGMEE) and stirred, and then filtered through a 0.2 μm filter to obtain a photosensitive resin composition. Prepared.

<Comparative Example 1>
The same as Example 1-7, except that no acrylic resin was used.
Specifically, it is as follows.
485.2 g of a 20.6% PGMEA solution of the resin (A1) described in Synthesis Example 1 and an esterified product of the compound represented by the formula B1 and 1,2-naphthoquinonediazide-5-sulfonyl chloride (Daitokemix Co., Ltd.) 30 g of manufactured PA-28), 26 g of epoxy resin EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.), 5 g of epoxy resin VG3101L (manufactured by Printec Co., Ltd.), 15 g of epoxy resin Epolite100MF (manufactured by Kyoei Co., Ltd.), and photosensitive resin composition 10 g of KBM-303 (manufactured by Shin-Etsu Silicone) to improve adhesion to the substrate, F-557 to prevent radial striations formed on the film when the photosensitive resin composition is spin coated. (Manufactured by DIC) 0.5 g of appropriate amount of diethylene glycol methyl ethyl ether (DEGMEE) After stirring to dissolve, then filtered through a 0.2μm filter to prepare a photosensitive resin composition.

<Comparative Example 2>
485.2 g of a 20.6% PGMEA solution of the resin (A1) described in Synthesis Example 1 and an esterified product of the compound represented by the formula B1 and 1,2-naphthoquinonediazide-5-sulfonyl chloride (Daitokemix Co., Ltd.) 30 g of manufactured PA-28), 50 g of epoxy resin EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.), 30 g of epoxy resin VG3101L (manufactured by Printec Co., Ltd.), 50 g of epoxy resin Epolite100MF (manufactured by Kyoei Co., Ltd.), and photosensitive resin composition 10 g of KBM-303 (manufactured by Shin-Etsu Silicone) to improve adhesion to the substrate, F-557 to prevent radial striations formed on the film when the photosensitive resin composition is spin coated. (Manufactured by DIC) 0.5 g of diethylene glycol methyl ethyl ether (DEGMEE) After stirring dissolved in, and filtered through a 0.2μm filter to prepare a photosensitive resin composition.

表１中において、樹脂組成物に含まれる各成分の配合量を示す数値のうち、かっこ外の数値は各成分の質量（ｇ）を、かっこ内の数値は樹脂組成物の全固形分（すなわち、溶媒を除く成分）を１００質量％としたときの各成分の配合割合（質量％）を、それぞれ示す。以下、表２においても同様である。

In Table 1, among the numerical values indicating the blending amount of each component contained in the resin composition, the numerical value outside the parentheses indicates the mass (g) of each component, and the numerical value within the parentheses indicates the total solid content of the resin composition (that is, , The component ratio excluding the solvent) is 100% by mass, and the blending ratio (% by mass) of each component is shown. The same applies to Table 2 below.

In each of Examples 1-7, a film having a low dielectric constant and high permeability could be obtained. Moreover, in Example 1-7, it turned out that a swelling rate is also low and chemical resistance is high. Furthermore, in Example 1-7, no crack occurred in the cured film of the photosensitive resin composition.
On the other hand, in Comparative Example 1 in which no acrylic resin was used, the swelling rate was high. In Comparative Example 2 in which no acrylic resin was used, although the swelling rate was low, cracks occurred in the cured film of the photosensitive resin composition.

10 substrate 12 counter substrate 14 liquid crystal layer 20, 50, 52, 54 insulating film 22, 24, 26 opening 30 transistor 31 gate electrode 32 source electrode 33 drain electrode 34 gate insulating film 35 semiconductor layer 40, 42 wiring 70 rewiring layer 72 Top layer wiring 74 Bump 80 Layer 90, 92 Alignment film 100 Electronic device

Claims (8)

A polymer represented by the following formula (1):
A first crosslinking agent that crosslinks with the polymer;
An acrylic resin that is a second cross-linking agent having a reactive group that cross-links with the polymer or the first cross-linking agent;
A photosensitive resin composition containing a photosensitive agent.

(In formula (1), l and m represent the molar content in the polymer, l + m = 1, and 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 30 carbon atoms, and A is a structural unit represented by the following formula (2a), (2b), (2c) or (2d))

(In Formula (2a) and Formula (2b), R ₅ , R ₆ and R ₇ are each independently an organic group having 1 to 18 carbon atoms) In the photosensitive resin composition of Claim 1,
The polymer has a structural unit represented by the formula (2a),
The first cross-linking agent has a cyclic ether group,
The photosensitive resin composition, wherein the second crosslinking agent is an acrylic resin having a reactive group that reacts with the cyclic ether group or the carboxyl group contained in the formula (2a). In the photosensitive resin composition of Claim 2,
The photosensitive resin composition, wherein the second crosslinking agent is an acrylic resin having a carboxyl group as the reactive group. In the photosensitive resin composition of Claim 3,
The first cross-linking agent is a photosensitive resin composition that is an epoxy compound. In the photosensitive resin composition in any one of Claims 1-4,
The photosensitive resin composition, wherein the second crosslinking agent is an acrylic resin containing a carbon ring.   An electronic device provided with the cured film of the photosensitive resin composition in any one of Claims 1-5. The electronic device according to claim 7.
In the liquid crystal display device, the cured film of the photosensitive resin composition is provided on a transistor formed on a substrate, and is an electronic device that is a planarizing film disposed between the transistor and a liquid crystal layer. The electronic device according to claim 7.
The cured film of the photosensitive resin composition is an electronic device for an interlayer insulating film provided between a multilayer wiring layer provided on a semiconductor substrate of a semiconductor device and a rewiring layer.

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