JP6075072B2 - Polymer, photosensitive resin composition and electronic device - Google Patents

Description

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

  In a circuit formation process such as a semiconductor integrated circuit, a resist film made of a photosensitive resin composition may be used. As a technique relating to such a resist film, for example, a technique described in Patent Document 1 can be cited. Patent Document 1 describes a photoresist composition containing an alkali-soluble resin and a photosensitizer.

Japanese Patent Laid-Open No. 2-146045

In recent years, it has been studied to use a photosensitive resin composition as a permanent film constituting an electronic device. In this case, after patterning the photosensitive resin composition by exposure and development, a permanent film is formed by curing the photosensitive resin composition.
However, the pattern may be deformed when the photosensitive resin composition is cured. The present inventors have found that in order to suppress such pattern deformation, it is important to appropriately design a polymer constituting the photosensitive resin composition.

According to the present invention, it is a copolymer represented by the following formula (1), and a polymer having a peak area at a molecular weight of 1000 or less in a molecular weight distribution curve obtained by GPC is 1% or less of the whole ,
A polymer film obtained by dissolving the polymer in propylene glycol monomethyl ether acetate and adjusting the solid content to 20% by weight on a silicon wafer by spin method, and soft baking at 110 ° C. for 100 seconds to form a polymer film , Impregnated with a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C., and visually measured the time until the polymer film was erased, and the calculated dissolution rate (Å / sec) was 500 Å / sec or more. A polymer is provided that is no greater than 20,000 K / sec .

（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）

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

（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)

Further, according to the present invention, a polymer represented by the above formula (1) and having a peak area at a molecular weight of 1000 or less in a molecular weight distribution curve obtained by GPC is 1% or less of the whole, and a crosslinking agent A photosensitive resin composition comprising a photosensitive agent ,
A polymer film prepared by dissolving the polymer in propylene glycol monomethyl ether acetate and adjusting the solid content to 20% by weight on a silicon wafer by spin method, and soft baking at 110 ° C. for 100 seconds to form a polymer film , Impregnated with a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C., and visually measured the time until the polymer film was erased, and the calculated dissolution rate (Å / sec) was 500 Å / sec or more. A photosensitive resin composition having a viscosity of 20,000 K / sec or less is provided.

Furthermore, according to the present invention, an electronic device with a permanent film formed by using a sensitive light-sensitive resin composition described above it is provided.

  According to the present invention, the operational reliability of an electronic device can be improved.

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 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 polymer according to the present embodiment is a copolymer represented by the following formula (1), and the peak area at a molecular weight of 1000 or less in the molecular weight distribution curve obtained by GPC is 1% or less of the whole.

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

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。以下、上記式（１）で示されるポリマーを、第１のポリマーとも称呼する。

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. Hereinafter, the polymer represented by the above formula (1) is also referred to as a first polymer.

By reducing the amount of the low molecular weight component of the polymer that is the copolymer represented by the above formula (1), the present inventors suppress the pattern deformation at the time of curing of the film formed using the polymer. I found out that I can do it. That is, the polymer according to the present embodiment is obtained based on such knowledge.
According to this embodiment, the first polymer represented by the above formula (1) has a peak area at a molecular weight of 1000 or less in a molecular weight distribution curve obtained by GPC of 1% or less of the whole. For this reason, the pattern shape of the film | membrane consisting of the photosensitive resin composition containing a 1st polymer can be made favorable. Therefore, it is possible to improve the operation reliability of an electronic device including the film as a permanent film.

  Hereinafter, the first polymer, the photosensitive resin composition, and the electronic device 100 according to the present embodiment will be described in detail.

(First polymer)
The first polymer according to this embodiment is a copolymer represented by the following formula (1).

In the formula (1), l and m represent the molar content (mol%) 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 (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.

The organic group having 1 to 30 carbon atoms constituting R ₁ , R ₂ , R ₃ and R ₄ may contain one or more selected from O, N, S, P and Si in the structure. Moreover, the organic group which comprises R < ₁ >, R < ₂ >, R < ₃ > and R < ₄ > does not have any acidic functional group. Thereby, control of the acid value in the first polymer can be facilitated.

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.
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, 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 the R _{5, R 6} and _{R 7,} O in their structure, N, S, may contain one or more selected from P and Si. 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. 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 has, for example, an acid value of 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 pH = 7.0. Based on the amount of KOH required for the titration, the acid value of the polymer (mg of KOH with respect to 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 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 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 the 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 alkali metal in the first polymer (ratio of the mass of alkali metal to the mass of polymer) is, for example, 10 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.
In addition, although the minimum of the alkali metal concentration in a 1st polymer is not specifically limited, this embodiment accept | permits the case where the alkali metal concentration in a 1st polymer is 0.01 mass 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 (1), 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 0, 1, or 2. R _{1 to} R ₄ are independent of each other. 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 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. To do. That is, the ring opening rate of the copolymer 1 is, for example, less than 50%. 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
Ring-opening rate (%) = ((A1-A2) / A1) × 100
Acetonitrile is used as an internal standard substance.

In particular,
(A) One of the metal alkoxide (B) alcohol as the base and the alkali metal hydroxide as the base is added to the reaction solution obtained by polymerizing the copolymer 1 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 them, 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 by mass or less, preferably 5 ppm by mass 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, followed by heating 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-type 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), (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.

(Photosensitive resin composition)
Next, the photosensitive resin composition according to the present embodiment will be described. The photosensitive resin composition according to the present embodiment includes the first polymer, a crosslinking agent, and a photosensitive agent.

(Crosslinking agent)
The crosslinking agent is thermosetting. As this crosslinking agent, a compound having a hetero ring as a reactive group is preferable, and a compound having a glycidyl group or an oxetanyl group is particularly preferable.
Examples of the compound having a glycidyl group include an epoxy resin, and any of the following epoxy resins can be used.
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). It is preferable that this epoxy resin is 20% by mass or more and 100% by mass or less of the entire crosslinking agent (excluding the second crosslinking agent described later). Especially, it is preferable to make this epoxy resin into 50 mass% or more of the whole crosslinking agent.

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.

Moreover, when the photosensitive resin composition is a negative type, in addition to the compound which has a heterocyclic ring as a reactive group mentioned above, the compound which has a multiple bond (for example, double bond) can be used. A compound having multiple bonds can be crosslinked, cured, and broken by an acid generated by a photoacid generator described below.
For example, you may use the compound which has any 1 or more types, such as an acryloyl group, a methacryloyl group, a vinyl group.
More specifically, any one or more of (meth) acryl-modified phenolic resin, (meth) acryloyl group-containing acrylic polymer, carboxyl group-containing (epoxy) acrylate, and the like can be used.

(Photosensitive agent)
When the photosensitive resin composition is a positive type, a photoactive compound can be used as the photosensitive agent, and 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 preferred 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.

Moreover, when the photosensitive resin composition is a negative type, it may contain what crosslinks a polymer by the effect | action of an acid as a 2nd crosslinking agent. This second cross-linking agent cross-links the polymer using an acid generated from the photo-acid generator as a catalyst, and is different from the cross-linking agent.
For example, a melamine type crosslinking agent, a urea type crosslinking agent, etc. are mentioned.
Examples of the melamine-based cross-linking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine, and the like, among which hexamethoxymethyl melamine is preferable.
Examples of the urea-based crosslinking agent include methylated urea resin, bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, bisbutoxymethylurea and the like, and methylated urea resin is particularly preferable.
Examples of commercially available methylated urea resins include MX-270, MX-280, MX-290 (manufactured by Sanwa Chemical Co., Ltd.), and the like.

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

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 of the resin composition (that is, the component excluding the solvent) is 100% by mass, the polymer described above is preferably contained in an amount of 30% by mass to 70% by mass, especially 40% by mass to 60% by mass. % Content is preferable.
Moreover, when the total solid content (namely, component except a solvent) of a resin composition is 100 mass%, it is preferable to contain a crosslinking agent 15 mass%-50 mass%, and especially contains 20 mass% or more. It is preferable.
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 photosensitive agent is preferably 5 to 40% by mass. More preferably, it is 10-30 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 of the resin composition (that is, the component excluding the solvent) is 100% by mass, the polymer described above is preferably contained in an amount of 30% by mass to 70% by mass, especially 40% by mass to 60% by mass. % Content is preferable.
Further, when the total solid content of the resin composition (that is, the component excluding the solvent) is 100% by mass, the crosslinking agent (except for the second crosslinking agent) is preferably contained in an amount of 15% by mass to 50% by mass, Especially, it is preferable to contain 20 mass% or more.
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, styrenated 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) pentapentaerythritol diphosphite, tris (2,4-di-t-butylphenyl phosphite), tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4′-biphenylenediphosphonite, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, bis- (2, 6-dicumylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, tris (mixed mono and di-nonylphenyl phosphite), bis (2 , 4-Di-t-butylphenyl) pentapentaerythritol-di-phosphite, bis (2,6-di-t-butyl) 4-methoxycarbonyl-ethyl - phenyl) pentaerythritol diphosphite, bis (2,6-di -t- butyl-4-octadecyloxycarbonyl ethyl - 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 to 5 weight% of the whole photosensitive resin composition.

Moreover, the photosensitive resin composition mentioned above may contain polyphenols.
Examples of polyphenols include phenol novolak, o-cresol novolak, p-cresol novolak, pt-butylphenol novolak, hydroxynaphthalene novolak, bisphenol A novolak, bisphenol F novolak, terpene modified novolak, dicyclopentadiene modified novolak, para Examples include xylene-modified novolak and polybutadiene-modified phenol, and any one or more of them can be used.

The following phenolic compounds can also be used.
o-cresol, m-cresol, p-cresol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, bisphenol A, B, C, E, F and G, 4,4 ', 4 " -Methylidinetrisphenol, 2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4-methylphenol, 4,4 '-[1- [4- [1- (4-hydroxyphenyl)] -1 -methylethyl] phenyl] ethylidene] bisphenol, 4,4 '-[1- [4- [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethylidene] bisphenol, 4,4', 4 " Ethylidinetrisphenol, 4- [bis (4-hydroxyphenyl) methyl] -2-ethoxyphenol, 4,4 ′-[(2-hydroxyphenyl) methylene] bis [2,3 -Dimethylphenol], 4,4 '-[(3-hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 4,4'-[(4-hydroxyphenyl) methylene] bis [2,6-dimethyl Phenol], 2,2 ′-[(2-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 2,2 ′-[(4-hydroxyphenyl) methylene] bis [3,5-dimethylphenol] 4,4 ′-[(3,4-dihydroxyphenyl) methylene] bis [2,3,6-trimethylphenol], 4- [bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) methyl]- 1,2-benzenediol, 4,6-bis [(3,5-dimethyl-4-hydroxyphenyl) methyl] -1,2,3-benzenetriol, 4,4 ′-[( -Hydroxyphenyl) methylene] bis [3-methylphenol], 4,4 ', 4 "-(3-methyl-1-propanyl-3-ylidine) trisphenol, 4,4', 4", 4 ''' -(1,4-phenylenedimethylidene) tetrakisphenol, 2,4,6-tris [(3,5-dimethyl-4-hydroxyphenyl) methyl] -1,3-benzenediol, 2,4,6-tris [(3,5-dimethyl-2-hydroxyphenyl) methyl] -1,3-benzenediol, 4,4 ′-[1- [4- [1- [4-hydroxy-3,5-bis [(hydroxy -3-methylphenyl) methyl] phenyl] -1-methylethyl] phenyl] ethylidene] bis [2,6-bis (hydroxy-3-methylphenyl) methyl] phenol and the like.
Among these compounds, 4,4 ′, 4 ″ -methylidynetrisphenol, 2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4-methylphenol, 4,4 ′-[1 -[4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 4,4 ′-[1- [4- [2- (4-hydroxyphenyl) -2-propyl] Phenyl] ethylidene] bisphenol, 4,4 ′, 4 ″ -ethylidinetrisphenol and the like are preferable. Any one or more of these can be used.
Particularly preferably, it is at least one of the following compounds.

In the photosensitive resin composition, when the solid content excluding the solvent is 100% by mass, the content of polyphenols is preferably 0% by mass to 30% by mass, and more preferably 3% by mass or more. It is preferable.
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 as follows.
(1) Relative dielectric constant After applying the photosensitive resin composition and exposing at 300 mJ / cm ² , the film was heated at 230 ° C. for 30 minutes, 250 ° C. for 60 minutes to form a film having a thickness of 2 μm, and then the frequency The relative dielectric constant measured at 10 kHz 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 1, for example.
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 136 seconds. Then, after exposing at 300 mJ / cm ² , post baking is performed by heating in an oven at 230 ° C. for 30 minutes, 250 ° C. for 60 minutes 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 is applied and exposed at 300 mJ / cm ^2, it is heated at 230 ° C. for 30 minutes, 250 ° C. for 60 minutes, and heated to form a film having a thickness of 2 μm. After the film is formed, the transmittance of light with a wavelength of 400 nm of the film 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 (number of rotations: 500 to 2500 rpm), and baked on a hot plate at 100 ° C. for 136 seconds. Then, a post-baking process is performed by heating at 230 ° C. for 60 minutes in an oven 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 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.
A photosensitive resin composition is spin-coated on a silicon wafer, and heated on a hot plate at 100 ° C. for 136 seconds to form a thin film A. The thin film B is obtained by exposure with an exposure apparatus so that the width of 10 μm lines and spaces is 1: 1 and developing with a 0.4 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 84 seconds.
Thereafter, after exposure at 300 mJ / cm ² , post baking is performed by heating in an oven at 230 ° C. for 30 minutes, 250 ° C. for 60 minutes, and this is designated as thin film C.
From the film thicknesses of the thin film A and the thin film B obtained by the above method, the remaining film ratio was calculated from the following equation.
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 A layer formed by spin coating and baked on a hot plate at 100 ° C. for 136 seconds is exposed to ultraviolet rays, developed with tetramethylammonium hydroxide, and again irradiated with ultraviolet rays of 300 mJ / The film thickness of the first film exposed to cm ² and then heated in an oven at 230 ° C. for 30 minutes, 250 ° C. for 60 minutes is defined as the first film thickness, and the first film is made of N-methylpyrrolidone. When the film thickness after immersion for 10 minutes at room temperature is the second film thickness, [{(second film thickness) − (first film thickness)} / (first film thickness)] × 100 ≦ 5 (%) is satisfied.

  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 configuration of the electronic device 100 according to the present embodiment will be described.
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 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, the wiring 40 connected to the drain electrode 33 and the alignment film 90 are 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 rewiring layer 80 is 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 rewiring layer 80 is provided on the insulating film 50. The rewiring layer 80 includes an insulating film 52 provided on the insulating film 50 so as to cover the uppermost wiring 72, a rewiring 70 provided on the insulating film 52, and on the insulating film 52 and the rewiring 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 70 is formed on the insulating film 52 and in the opening 24, and is connected to the uppermost layer wiring 72. The insulating film 54 is provided with an opening 26 connected to the rewiring 70.
The insulating film 52 and the insulating film 54 are composed of permanent films made of the photosensitive resin composition. The insulating film 52 is obtained, for example, by forming the opening 24 by exposing and developing the photosensitive resin composition applied on the insulating film 50, and then heat-curing the opening 24. The insulating film 54 is obtained by, for example, forming the opening 26 by exposing and developing the photosensitive resin composition applied on the insulating film 52, and then heat-curing the opening 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.

（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）
２．
１．に記載のポリマーにおいて、
重量平均分子量Ｍｗ／数平均分子量Ｍｎは、１．５以上２．５以下であるポリマー。
３．
１．または２．に記載のポリマーにおいて、
重量平均分子量Ｍｗは、５，０００以上３０，０００以下であるポリマー。
４．
１．〜３．いずれかひとつに記載のポリマーにおいて、
前記ポリマーをプロピレングリコールモノメチルエーテルアセテートに溶解させ、固形分２０重量％に調整したポリマー溶液を、シリコンウェハ上にスピン方式で塗布し、これを１１０℃で１００秒間ソフトベークして得られるポリマー膜を、２３℃で２．３８％のテトラメチルアンモニウムハイドロオキサイド水溶液に含浸させ、視覚的に前記ポリマー膜が消去するまでの時間を測定し、算出された溶解速度（Å／秒）が５００Å／秒以上２０,０００Å／秒以下であるポリマー。
５．
１．〜４．いずれかひとつに記載のポリマーにおいて、
上記式（１）で示される共重合体には、上記式（２ａ）により示される構造単位、および上記式（２ｂ）により示される構造単位が含まれるポリマー。
６．
下記式（１）で示される共重合体であり、かつＧＰＣにより得られる分子量分布曲線において分子量１０００以下におけるピーク面積が全体の１％以下であるポリマーと、
架橋剤と、
感光剤と、
を備える感光性樹脂組成物。

（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）
７．
６．に記載の感光性樹脂組成物において、
前記ポリマーの重量平均分子量Ｍｗ／数平均分子量Ｍｎは、１．５以上２．５以下である感光性樹脂組成物。
８．
６．または７．に記載の感光性樹脂組成物において、
前記ポリマーの重量平均分子量Ｍｗは、５，０００以上３０，０００以下である感光性樹脂組成物。
９．
６．〜８．いずれかひとつに記載の感光性樹脂組成物において、
上記式（１）で示される共重合体には、上記式（２ａ）により示される構造単位、および上記式（２ｂ）により示される構造単位が含まれる感光性樹脂組成物。
１０．
６．〜９．いずれか一項に記載の感光性樹脂組成物を用いて形成される永久膜を備える電子装置。 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.
Hereinafter, examples of the reference form will be added.
1.
A polymer represented by the following formula (1) and having a peak area at a molecular weight of 1000 or less in a molecular weight distribution curve obtained by GPC of 1% or less.

(In the formula (1),
l and m represent the molar content in the polymer,
l + m = 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 30 carbon atoms;
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)
2.
1. In the polymer described in
The polymer whose weight average molecular weight Mw / number average molecular weight Mn is 1.5 or more and 2.5 or less.
3.
1. Or 2. In the polymer described in
The polymer whose weight average molecular weight Mw is 5,000 or more and 30,000 or less.
4).
1. ~ 3. In the polymer described in any one of the above,
A polymer film prepared by dissolving the polymer in propylene glycol monomethyl ether acetate and adjusting the solid content to 20% by weight on a silicon wafer by spin method, and soft baking at 110 ° C. for 100 seconds to form a polymer film , Impregnated with a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C., and visually measured the time until the polymer film was erased, and the calculated dissolution rate (Å / sec) was 500 Å / sec or more. A polymer that is 20,000 K / sec or less.
5.
1. ~ 4. In the polymer described in any one of the above,
The copolymer represented by the above formula (1) is a polymer containing the structural unit represented by the above formula (2a) and the structural unit represented by the above formula (2b).
6).
A polymer represented by the following formula (1) and having a peak area at a molecular weight of 1000 or less in a molecular weight distribution curve obtained by GPC of 1% or less of the whole;
A crosslinking agent;
A photosensitizer,
A photosensitive resin composition comprising:

(In the formula (1),
l and m represent the molar content in the polymer,
l + m = 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 30 carbon atoms;
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)
7).
6). In the photosensitive resin composition described in
The photosensitive resin composition whose weight average molecular weight Mw / number average molecular weight Mn of the said polymer is 1.5-2.5.
8).
6). Or 7. In the photosensitive resin composition described in
The photosensitive resin composition whose weight average molecular weight Mw of the said polymer is 5,000 or more and 30,000 or less.
9.
6). ~ 8. In the photosensitive resin composition according to any one of the above,
The photosensitive resin composition in which the copolymer shown by said Formula (1) contains the structural unit shown by said Formula (2a), and the structural unit shown by said Formula (2b).
10.
6). ~ 9. An electronic device comprising a permanent film formed using the photosensitive resin composition according to any one of the above.

  Next, examples of the present invention will be described.

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 solution was purged with nitrogen for 10 minutes to remove oxygen, then heated to 60 ° C. with stirring and heated for 16 hours. Next, after adding MEK (320 g), this was added to a suspension of sodium hydroxide (7.5 g, 0.188 mol) and butanol (463.1 g, 6.25 mol) and mixed at 45 ° C. for 3 hours. . The mixed solution was cooled to 40 ° C. and treated with formic acid (88 wt% aqueous solution, 215.8 g, 4.14 mol) to carry out proton addition. Thereafter, MEK and water were added to this mixed solution, and the aqueous layer was separated to remove inorganic residues. Subsequently, extraction operation was repeated until methanol and hexane were added and the content of low nuclei having a molecular weight of 1000 or less was 1% or less. Further, PGMEA (550 g) was added, and methanol / butanol in the system was distilled off under reduced pressure until the residual amount was less than 1%. Subsequently, 600 g of the obtained reaction solution was replaced with PGMEA. As a result, 730.3 g (polymer solution) of a PGMEA solution having a polymer solid content of 20% by weight was obtained (GPC Mw = 15,300).

  To the obtained polymer solution, 25 parts by weight of a photosensitizer TrisP 3M6C-2-201 (manufactured by Toyo Gosei Co., Ltd.) and 20 parts by weight of TMPTGE were added and dissolved with respect to 100 parts by weight of polymer solids in the polymer solution. Thereby, a photosensitive resin composition was obtained.

(Example 2)
In a suitably sized reaction vessel equipped with stirrer, condenser, maleic anhydride (MA, 122.4 g, 1.25 mol), 2-norbornene (NB, 117.6 g, 1.25 mol) and 2,2 ′ -Azobisisobutyronitrile (AIBN, 4.10 g, 25.0 mmol) was weighed and dissolved in methyl ethyl ketone (MEK, 39.0 g) and toluene (116.9 g). The solution was purged with nitrogen for 10 minutes to remove oxygen, and then heated to 60 ° C. with stirring to initiate the reaction. After the reaction started, MEK (80.0 g) was added after 3 hours, and AIBN (4.10 g, 25.0 mmol) and MEK (47.6 g) were added after 8 hours. 22 hours after the start of the reaction, it was diluted with MEK (268.4 g), added to a suspension of sodium hydroxide (7.5 g, 0.188 mol) and butanol (463.1 g, 6.25 mol), and then at 45 ° C. for 3 hours. Mixed. The mixed solution was cooled to 40 ° C. and treated with formic acid (88 wt% aqueous solution, 215.8 g, 4.14 mol) to carry out proton addition. Thereafter, MEK and water were added to this mixed solution, and the aqueous layer was separated to remove inorganic residues. Subsequently, extraction operation was repeated until methanol and hexane were added and the content of low nuclei having a molecular weight of 1000 or less was 1% or less. Further, PGMEA was added, and methanol / butanol in the system was distilled off under reduced pressure until the residual amount was less than 1%, and the solvent was replaced with PGMEA. As a result, 994.4 g (polymer solution) of a PGMEA solution having a polymer solid content of 20% by weight (GPC Mw = 17,700) was obtained.

  To the obtained polymer solution, 25 parts by weight of a photosensitizer TrisP 3M6C-2-201 (manufactured by Toyo Gosei Co., Ltd.) and 20 parts by weight of TMPTGE were added and dissolved with respect to 100 parts by weight of polymer solids in the polymer solution. Thereby, a photosensitive resin composition was obtained.

(Example 3)
In a suitably sized reaction vessel equipped with stirrer, condenser, maleic anhydride (MA, 122.4 g, 1.25 mol), 2-norbornene (NB, 117.6 g, 1.25 mol) and 2,2 ′ -Azobisisobutyronitrile (AIBN, 8.20 g, 50.0 mmol) was weighed and dissolved in THF (153.0 g) and toluene (77.7 g). The solution was purged with nitrogen for 10 minutes to remove oxygen, and then heated to 60 ° C. with stirring to initiate the reaction. After 16 hours from the start of the reaction, THF (320 g) was added, and then added to a suspension of sodium hydroxide (7.5 g, 0.188 mol) and butanol (463.1 g, 6.25 mol). Mixed for hours. The mixture was cooled to 40 ° C. and treated with hydrochloric acid (35 wt% aqueous solution, 157.6 g, 4.14 mol) to carry out protonation. Thereafter, MEK and water were added to this mixed solution, and the aqueous layer was separated to remove inorganic residues. Subsequently, methanol and hexane were added, and liquid-liquid extraction was repeated until the content of low nuclei having a molecular weight of 1000 or less became 1% or less. Further, PGMEA was added, and methanol / butanol in the system was distilled off under reduced pressure until the residual amount was less than 1%, and the solvent was replaced with PGMEA. As a result, 643.4 g (polymer solution) of a PGMEA solution having a polymer solid content of 20% by weight was obtained (GPC Mw = 10,800).

  To the obtained polymer solution, 25 parts by weight of a photosensitizer TrisP 3M6C-2-201 (manufactured by Toyo Gosei Co., Ltd.) and 20 parts by weight of TMPTGE were added and dissolved with respect to 100 parts by weight of polymer solids in the polymer solution. Thereby, a photosensitive resin composition was obtained.

Example 4
In a suitably sized reaction vessel equipped with stirrer and condenser, maleic anhydride (MA, 244.9 g, 2.50 mol), 2-norbornene (NB, 313.5 g, 2.50 mol) and dimethyl 2,2 '-Azobis (2-methylpropionate) (23.0 g, 50.0 mmol) was weighed and dissolved in methyl ethyl ketone (MEK, 301.6 g) and toluene (155.4 g). The solution was purged with nitrogen for 10 minutes to remove oxygen, then heated to 60 ° C. with stirring and heated for 16 hours. After the addition of MEK (640 g), sodium hydroxide of (10.0 g, 0.250 mol), butanol (926.3g, 12.5mol), was added to a suspension of toluene (960 g), at 45 ° C. Mixed for 3 hours. The mixed solution was cooled to 40 ° C. and treated with formic acid (88 wt% aqueous solution, 215.8 g, 4.14 mol) to carry out proton addition. Thereafter, MEK and water were added to this mixed solution, and the aqueous layer was separated to remove inorganic residues. Subsequently, extraction operation was repeated until methanol and hexane were added and the content of low nuclei having a molecular weight of 1000 or less was 1% or less. Further, PGMEA was added, and methanol / butanol in the system was distilled off under reduced pressure until the residual amount was less than 1%, and the solvent was replaced with PGMEA. Next, the reaction solution was heated at 125 ° C. for 3 hours, and then the solvent was replaced with PGMEA. As a result, 2144.3 g of a 20 wt% polymer solution was obtained (GPC Mw = 13,500).

  To the obtained polymer solution, 25 parts by weight of a photosensitizer TrisP 3M6C-2-201 (manufactured by Toyo Gosei Co., Ltd.) and 20 parts by weight of TMPTGE were added and dissolved with respect to 100 parts by weight of polymer solids in the polymer solution. Thereby, a photosensitive resin composition was obtained.

(Example 5)
In a suitably sized reaction vessel equipped with stirrer and condenser, maleic anhydride (MA, 244.9 g, 2.50 mol), 2-norbornene (NB, 313.5 g, 2.50 mol) and dimethyl 2,2 '-Azobis (2-methylpropionate) (23.0 g, 50.0 mmol) was weighed and dissolved in methyl ethyl ketone (MEK, 301.6 g) and toluene (155.4 g). The solution was purged with nitrogen for 10 minutes to remove oxygen, then heated to 60 ° C. with stirring and heated for 16 hours. After the addition of MEK (640 g), sodium hydroxide of (12.5g, 0.313mol), butanol (926.3g, 12.5mol), was added to a suspension of toluene (960 g), at 45 ° C. Mixed for 3 hours. The mixed solution was cooled to 40 ° C. and treated with formic acid (88 wt% aqueous solution, 215.8 g, 4.14 mol) to carry out proton addition. Thereafter, MEK and water were added to this mixed solution, and the aqueous layer was separated to remove inorganic residues. Subsequently, extraction operation was repeated until methanol and hexane were added and the content of low nuclei having a molecular weight of 1000 or less was 1% or less. Further, PGMEA was added, and methanol / butanol in the system was distilled off under reduced pressure until the residual amount was less than 1%, and the solvent was replaced with PGMEA. Next, the reaction solution was heated at 125 ° C. for 3 hours, and then the solvent was replaced with PGMEA. This gave 2189.4 g of a 20 wt% polymer solution (GPC Mw = 13,300).

  To the obtained polymer solution, 25 parts by weight of a photosensitizer TrisP 3M6C-2-201 (manufactured by Toyo Gosei Co., Ltd.) and 20 parts by weight of TMPTGE were added and dissolved with respect to 100 parts by weight of polymer solids in the polymer solution. Thereby, a photosensitive resin composition was obtained.

(Comparative Example 1)
In a suitably sized reaction vessel equipped with stirrer, condenser, maleic anhydride (MA, 122.4 g, 1.25 mol), 2-norbornene (NB, 117.6 g, 1.25 mol) and 2,2 ′ -Azobisisobutyronitrile (AIBN, 4.10 g, 25.0 mmol) was weighed and dissolved in THF (39.0 g) and toluene (116.9 g). The solution was purged with nitrogen for 10 minutes to remove oxygen, and then heated to 60 ° C. with stirring to initiate the reaction. After the reaction started, MEK (80.0 g) was added when 3 hours passed, and AIBN (4.10 g, 25.0 mmol) and THF (49.2 g) were added when 8 hours passed. After 22 hours from the start of the reaction, the reaction mixture was diluted with MEK (266.7 g) and added to a suspension of sodium hydroxide (55.0 g, 1.38 mol) and butanol (463.1 g, 6.25 mol), and then at 45 ° C. for 3 hours. Mixed. The mixture was cooled to 40 ° C. and treated with hydrochloric acid (35 wt% aqueous solution, 157.6 g, 4.14 mol) to carry out protonation. Thereafter, THF and water were added to the mixed solution, and the aqueous layer was separated to remove inorganic residues. Subsequently, methanol and hexane were added and the organic layer was separated to remove unreacted monomers. Further, PGMEA (700 g) was added, and methanol in the system was distilled off under reduced pressure until the residual amount was less than 1%. Next, the obtained reaction solution was diluted with PGMEA to 20% by weight and heated at 125 ° C. for 8 hours, and then the solvent was replaced with PGMEA. As a result, 895.5 g (polymer solution) of a PGMEA solution having a polymer solid content of 20% by weight (GPC Mw = 13,900) was obtained.

  To the obtained polymer solution, 25 parts by weight of a photosensitizer TrisP 3M6C-2-201 (manufactured by Toyo Gosei Co., Ltd.) and 20 parts by weight of TMPTGE were added and dissolved with respect to 100 parts by weight of polymer solids in the polymer solution. Thereby, a photosensitive resin composition was obtained.

(Molecular weight and dispersity)
The number average molecular weight / weight average molecular weight (Mn · Mw) and dispersity (PDI: Mw / Mn) of the polymers synthesized in each Example and each Comparative Example are obtained from a standard polystyrene (PS) calibration curve obtained by GPC measurement. It calculated using the calculated | required polystyrene conversion value.
The measurement conditions were 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 / ml Table 1 shows the results.

(Low molecular weight component)
The amount of the low molecular weight component of the polymer synthesized in each Example and each Comparative Example is the ratio of the total area of components corresponding to a molecular weight of 1000 or less in the area of the entire molecular weight distribution in the data on the molecular weight obtained by GPC measurement. Asked.
Table 1 shows the results.

(Pattern flow)
The photosensitive resin composition adjusted based on each Example and each comparative example was apply | coated with the spin system, and it soft-baked with a 100 degreeC hotplate for 90 second, and formed into a film. Next, this film was exposed to ultraviolet rays and developed with tetramethylammonium hydroxide to form a 10 μm hole pattern. Next, the entire surface exposed (bleached) with ultraviolet rays again was cured by baking in an oven at 200 ° C. for 60 minutes. The rate of dimensional change between the top and bottom of the hole pattern before and after curing was calculated based on the following formula. In the following formula, CD (Critical Dimension) indicates the width of the hole.
Dimensional change rate (%) = {(Top CD before curing) / (Bottom CD before curing)} / {(Top CD after curing) / (Bottom CD after curing)}
Evaluation was made with a dimensional change rate of 1.5 or less as ◯, a dimensional change rate of 1.5 to 2.0 as Δ, and a value exceeding 2.0 as ×. Table 1 shows the results.

As shown in Table 1, in Examples 1 to 5, the ratio of the total area of the components corresponding to the molecular weight of 1000 or less in the total area of the molecular weight distribution was 1% or less. Further, the dispersity Mw / Mn was in the range of 1.5 to 2.5. In Examples 1 to 5, good results were obtained for the pattern flow. That is, in the Example, it turns out that the pattern deformation at the time of film hardening can be suppressed.
On the other hand, in Comparative Example 1, the ratio of the total area of components corresponding to a molecular weight of 1000 or less in the total area of the molecular weight distribution exceeded 1%. Further, the degree of dispersion Mw / Mn exceeded 2.5. In Comparative Example 1, good results were not obtained for the pattern flow. That is, in the comparative example, the pattern deformation at the time of film hardening could not be sufficiently suppressed.

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 72 top Upper wiring 74 Bump 80 Rewiring layer 90, 92 Alignment film 100 Electronic device

Claims (9)

A polymer represented by the following formula (1) and having a peak area at a molecular weight of 1000 or less in a molecular weight distribution curve obtained by GPC of 1% or less ,
A polymer film obtained by dissolving the polymer in propylene glycol monomethyl ether acetate and adjusting the solid content to 20% by weight on a silicon wafer by spin method, and soft baking at 110 ° C. for 100 seconds to form a polymer film , Impregnated with a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C., and visually measured the time until the polymer film was erased, and the calculated dissolution rate (Å / sec) was 500 Å / sec or more. A polymer that is 20,000 K / sec or less .

(In the formula (1),
l and m represent the molar content in the polymer,
l + m = 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 30 carbon atoms;
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) The polymer of claim 1, wherein
The polymer whose weight average molecular weight Mw / number average molecular weight Mn is 1.5 or more and 2.5 or less. The polymer according to claim 1 or 2,
The polymer whose weight average molecular weight Mw is 5,000 or more and 30,000 or less. In the polymer according to any one of claims 1 to 3 ,
The copolymer represented by the above formula (1) is a polymer containing the structural unit represented by the above formula (2a) and the structural unit represented by the above formula (2b). A polymer represented by the following formula (1) and having a peak area at a molecular weight of 1000 or less in a molecular weight distribution curve obtained by GPC of 1% or less of the whole;
A crosslinking agent;
A photosensitizer,
A photosensitive resin composition comprising,
A polymer film prepared by dissolving the polymer in propylene glycol monomethyl ether acetate and adjusting the solid content to 20% by weight on a silicon wafer by spin method, and soft baking at 110 ° C. for 100 seconds to form a polymer film , Impregnated with a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C., and visually measured the time until the polymer film was erased, and the calculated dissolution rate (Å / sec) was 500 Å / sec or more. A photosensitive resin composition having a viscosity of 20,000 K / sec or less .

(In the formula (1),
l and m represent the molar content in the polymer,
l + m = 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 30 carbon atoms;
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 5 ,
The photosensitive resin composition whose weight average molecular weight Mw / number average molecular weight Mn of the said polymer is 1.5-2.5. In the photosensitive resin composition of Claim 5 or 6 ,
The photosensitive resin composition whose weight average molecular weight Mw of the said polymer is 5,000 or more and 30,000 or less. In the photosensitive resin composition according to any one of claims 5-7,
The photosensitive resin composition in which the copolymer shown by said Formula (1) contains the structural unit shown by said Formula (2a), and the structural unit shown by said Formula (2b). An electronic device comprising a permanent film formed using the photosensitive resin composition according to any one of claims 5 to 8 .

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