JP2017049372A - Photosensitive resin composition, production method of cured film and cured film - Google Patents

Abstract

A photosensitive resin composition, a cured film obtained by curing the photosensitive resin composition, and a cured film obtained by curing the photosensitive resin composition, wherein the cured film is highly sensitive and exhibits excellent corrosion resistance and low dielectric constant. A method for manufacturing a membrane is provided.
A polymer component A1 containing a polymer A1-1 containing a structural unit a1 having a group in which an acid group is protected with an acid-decomposable group, a photoacid generator B1, and a solvent C. The polymer component A1 contains a structural unit p1 represented by a specific general formula (I), (II) or (III), or
A polymer component A2 containing a polymer A2-1 containing a structural unit a2 having an acid group, a quinonediazide compound B2 and a solvent C, wherein the polymer component A2 has a specific formula (IV), The photosensitive resin composition containing the structural unit p2 represented by (V) or (VI).
[Selection figure] None

Description

  The present invention relates to a photosensitive resin composition, a method for producing a cured film, and a cured film.

Image display devices such as liquid crystal display devices and organic electroluminescence display devices, and input devices such as touch panels are generally provided with a patterned interlayer insulating film.
For the formation of this interlayer insulating film, photosensitive resin compositions are widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained.

  For example, Patent Document 1 discloses, as a photosensitive resin composition, “(A) an acetal resin, (B) a photoacid generator, and (C) a solvent. A structural unit (a1) having a structure for generating a carboxyl group, a structural unit (a2) having a carboxyl group or a phenolic hydroxyl group, a structural unit (a3) having an epoxy group or an oxetanyl group, and a hydroxyl group or an alkyleneoxy group “A photosensitive resin composition which is a polymer containing the structural unit (a4) and having an acetal structure or a ketal structure” is described ([Claim 1]).

JP2011-221494A

  In recent years, an interlayer insulating film having higher characteristics has been demanded in response to needs for higher functionality and smaller size of various display devices. In particular, since the interlayer insulating film is a member that is in direct contact with a metal material such as a wiring or an electrode, it is demanded that such a metal is difficult to corrode (excellent corrosion resistance). Further, in order to further reduce the parasitic capacitance, further reduction of the relative dielectric constant is also demanded. Further, it is naturally required to have sufficient sensitivity for forming a fine pattern.

  Under these circumstances, the present inventors examined the photosensitive resin composition described in Patent Document 1, and as a result, the corrosion resistance and the low dielectric constant of the obtained cured film (interlayer insulating film) are not always the levels required recently. It became clear that it was not satisfied.

  Therefore, in view of the above circumstances, the present invention cures the photosensitive resin composition, the photosensitive resin composition having high sensitivity and the obtained cured film exhibiting excellent corrosion resistance and low dielectric constant. It is an object of the present invention to provide a cured film and a method for producing the cured film.

As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by using a polymer containing a structural unit represented by a specific general formula.
That is, the present inventors have found that the above problem can be solved by the following configuration.

(1) A polymer component A1 containing a polymer A1-1 containing a structural unit a1 having a group in which an acid group is protected with an acid-decomposable group, a photoacid generator B1, and a solvent C.
The photosensitive resin composition in which the said polymer component A1 contains the structural unit p1 represented by general formula (I), (II) or (III) mentioned later.
(2) containing polymer component A2 containing polymer A2-1 containing structural unit a2 having an acid group, quinonediazide compound B2, and solvent C,
The photosensitive resin composition in which the said polymer component A2 contains the structural unit p2 represented by general formula (IV), (V), or (VI) mentioned later.
(3) The photosensitive resin composition as described in said (1) whose R in said general formula (I)-(III) is an acid-decomposable group.
(4) The process of apply | coating the photosensitive resin composition in any one of said (1)-(3) to a board | substrate,
Removing the solvent C from the applied photosensitive resin composition;
Exposing the photosensitive resin composition from which the solvent C has been removed with actinic rays;
Developing the exposed photosensitive resin composition with a developer;
A process for producing a cured film comprising heat-treating the developed photosensitive resin composition to obtain a cured film.
(5) The cured film formed by hardening the photosensitive resin composition in any one of said (1)-(3).
(6) The cured film according to (5), which is one type selected from the group consisting of an insulating film, a protective film, and a planarizing film.

  As shown below, according to the present invention, the photosensitive resin composition having high sensitivity and the cured film obtained exhibits excellent corrosion resistance and low dielectric constant, and the photosensitive resin composition is cured. And a method for producing the cured film can be provided.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, “(meth) acrylate” is a notation representing “acrylate” or “methacrylate”, “(meth) acryl” is a notation representing “acryl” or “methacryl”, and “(meth) The “) acryloyl” is a notation representing “acryloyl” or “methacryloyl”.
The “photosensitive resin composition” is also simply referred to as “composition”.

The photosensitive resin composition according to the first aspect of the present invention (hereinafter also referred to simply as “first aspect of the present invention”) has a structural unit a1 having a group in which an acid group is protected with an acid-decomposable group. A polymer component A1 containing a polymer A1-1 containing, a photoacid generator B1, and a solvent C. Here, the polymer component A1 includes a structural unit p1 represented by the following general formula (I), (II) or (III).
The photosensitive resin composition according to the second aspect of the present invention (hereinafter, also simply referred to as “second aspect of the present invention”) contains a polymer A2-1 containing a structural unit a2 having an acid group. Contains polymer component A2, quinonediazide compound B2, and solvent C. Here, the polymer component A2 includes a structural unit p2 represented by the following general formula (IV), (V), or (VI).

As described above, the photosensitive resin composition according to the first aspect of the present invention and the second aspect of the present invention contains a polymer component containing the structural unit p1 or p2 represented by a specific general formula. Due to such a configuration, it is considered that the obtained cured film exhibits excellent corrosion resistance and low dielectric constant. The reason is not clear, but it is presumed that it is as follows.
First, when the photosensitive resin composition described in Patent Document 1 was used, the present inventors examined the cause of insufficient corrosion resistance and low dielectric constant of the resulting cured film. As a result, when the photosensitive resin composition described in Patent Document 1 is heat-treated to produce a cured film, the polymer has a carboxyl group (including a carboxyl group generated from an acid-decomposable group) and an epoxy group. At this time, since some of the carboxyl groups remained without reacting with the epoxy group, it was estimated that the remaining carboxyl groups corroded the metal. In addition, when an epoxy group and a carboxyl group react with each other, a secondary alcohol hydroxyl group is generated as follows, and this secondary alcohol hydroxyl group is estimated to increase the dielectric constant.

The present invention is based on the above findings, and is specifically characterized in that a structure in which a carboxyl group disappears in the process of producing a cured film.
That is, in the present invention, since the polymer has a carboxyl group or a protected carboxyl group in a form represented by a specific general formula described later, an imide ring is generated by a cyclization reaction when heat-treated, for example, as follows. The carboxyl group disappears. As a result, it is considered that a cured film exhibiting excellent corrosion resistance and a low dielectric constant can be obtained without causing the above-described metal corrosion and increase in relative dielectric constant.

[First Aspect of the Present Invention]
The photosensitive resin composition according to the first aspect of the present invention includes a polymer component A1 containing a polymer A1-1 containing a structural unit a1 having a group in which an acid group is protected by an acid-decomposable group, and light. An acid generator B1 and a solvent C are contained. Here, the polymer component A1 includes a structural unit p1 represented by the following general formula (I), (II) or (III).
Hereinafter, each component will be described in detail.

[Polymer component A1]
The polymer component A1 is a polymer component containing a polymer A1-1 containing a structural unit a1 having a group in which an acid group is protected with an acid-decomposable group. Moreover, polymer component A1 contains the structural unit p1 represented by general formula (I), (II), or (III) mentioned later.
Here, in the polymer component A1, the deprotection reaction of the acid-decomposable group in the polymer A1-1 proceeds by the action of a catalytic amount of an acidic substance generated from the photoacid generator B1 described later, and the acid group is This increases the solubility in the developer.

  The polymer component A1 includes other polymer A1-2 added as necessary in addition to the polymer A1-1. The polymer component A1 may contain two or more types of polymers A1-1, and may contain two or more types of polymers A1-2 when containing the polymer A1-2. .

  The polymer A1-2 that may be contained in the polymer component A1 is not particularly limited as long as it does not include the “structural unit a1 having a group in which an acid group is protected by an acid-decomposable group”. And polymers containing “other structural unit” and “structural unit p1” to be described later.

In the present invention, the polymer contained in the polymer component A1 is preferably an addition polymerization type polymer, and is a polymer containing structural units derived from (meth) acrylic acid and / or its ester. Is more preferable.
Moreover, you may have structural units other than the structural unit derived from (meth) acrylic acid and / or its ester, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc.
The “structural unit derived from (meth) acrylic acid and / or its ester” is also referred to as “acrylic structural unit”.
The same applies to the polymer component A2 in the second embodiment of the present invention described later.

As described above, the polymer A1-1 includes “structural unit a1 having a group in which an acid group is protected by an acid-decomposable group”.
First, “the structural unit a1 having a group in which an acid group is protected by an acid-decomposable group” included in the polymer A1-1, and “other structural unit” that may be included in the polymer A1-1. Will be described.

<Structural unit a1>
Hereinafter, the structural unit a1 having a group in which an acid group is protected with an acid-decomposable group will be described, but the present invention is not limited thereto. In addition, when the polymer component A1 contains the polymer A1-1 having the structural unit a1, an extremely sensitive chemical amplification type (mainly positive type) resin composition can be obtained.

As the “group in which the acid group is protected with an acid-decomposable group” in the present invention, those known as an acid group and an acid-decomposable group can be used, and are not particularly limited.
Preferred examples of the acid group include a carboxyl group and a phenolic hydroxyl group.
The acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an acetal functional group such as an ester structure, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group, which will be described later), or a group that is relatively decomposed by an acid. Difficult groups (for example, tertiary alkyl groups such as tert-butyl ester groups and tertiary alkyl carbonate groups such as tert-butyl carbonate groups).

The structural unit a1 having a group in which an acid group is protected with an acid-decomposable group is a structural unit having a protected carboxyl group in which a carboxyl group is protected with an acid-decomposable group (hereinafter referred to as “structural unit having a protected carboxyl group” Or a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected with an acid-decomposable group (hereinafter also referred to as “structural unit having a protected phenolic hydroxyl group”).
Hereinafter, the structural unit a1-A having a protected carboxyl group and the structural unit a1-B having a protected phenolic hydroxyl group will be described in order.

<< Structural Unit a1-A Having a Protected Carboxyl Group >>
The structural unit a1-A having a protected carboxyl group is a structural unit having a protected carboxyl group in which the carboxyl group of the structural unit having a carboxyl group is protected by the acid-decomposable group described above.
There is no restriction | limiting in particular as a structural unit which has the said carboxyl group which can be used for the structural unit a1-A which has the said protected carboxyl group, A well-known structural unit can be used. For example, the structural unit a1-A-1 derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, or unsaturated tricarboxylic acid, or ethylenic The structural unit a1-A-2 which has both the group which has an unsaturated bond, and the structure derived from an acid anhydride is mentioned.
Hereinafter, a constitutional unit a1-A-1 derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, a group having an ethylenically unsaturated bond, and a structure derived from an acid anhydride. The units a1-A-2 will be described in order.

(Structural unit a1-A-1 derived from unsaturated carboxylic acid having at least one carboxyl group in the molecule)
Examples of the unsaturated carboxylic acid used in the present invention as the structural unit a1-A-1 derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule include those described in JP-A-2014-238438. And the compounds described in paragraph 0043.
Among them, from the viewpoint of developability, in order to form the structural unit a1-1-1, acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acryloyloxy It is preferable to use ethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, or an anhydride of an unsaturated polyvalent carboxylic acid, and acrylic acid, methacrylic acid, 2- (meth) acryloyloxy More preferably, ethylhexahydrophthalic acid is used.
The structural unit a1-A-1 derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule may be composed of one kind alone, or may be composed of two or more kinds. Good.

(Structural unit a1-A-2 having both a group having an ethylenically unsaturated bond and a structure derived from an acid anhydride)
The structural unit a1-A-2 having both a group having an ethylenically unsaturated bond and a structure derived from an acid anhydride is a hydroxyl group and an acid anhydride present in the structural unit having a group having an ethylenically unsaturated bond. It is preferable that it is a unit derived from the monomer obtained by reacting.
As the acid anhydride, known ones can be used, and specifically, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, etc. Dibasic acid anhydrides; acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, and the like. Among these, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferable from the viewpoint of developability.
The reaction rate of the acid anhydride with respect to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, from the viewpoint of developability.

(Acid-decomposable group that can be used for the structural unit a1-A having a protected carboxyl group)
As the acid-decomposable group that can be used for the structural unit a1-A having the protected carboxyl group, the acid-decomposable group described above can be used.
Among these acid-decomposable groups, the carboxyl group is a protected carboxyl group protected in the form of an acetal, so that the basic physical properties of the resin composition, particularly sensitivity and pattern shape, contact hole formation, and storage of the resin composition It is preferable from the viewpoint of stability. Furthermore, among the acid-decomposable groups, it is more preferable from the viewpoint of sensitivity that the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following formula a1-Z. In addition, when the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following formula a1-Z, the entire protected carboxyl group is-(C = O) -O-CR ¹⁰¹ R ¹⁰² ( OR ¹⁰³ ).

(A1-Z)

In formula a1-Z, R ¹⁰¹ and R ¹⁰² each independently represents a hydrogen atom or a hydrocarbon group. However, the case where both R ¹⁰¹ and R ¹⁰² are hydrogen atoms is excluded. R ¹⁰³ represents a hydrocarbon group. R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be linked to form a cyclic ether. Examples of the hydrocarbon group include an aliphatic hydrocarbon group (preferably an alkyl group), an aromatic hydrocarbon group, and the like.

In the above formula a1-Z, when R ¹⁰¹ , R ¹⁰² or R ¹⁰³ represents an alkyl group, it may be linear, branched or cyclic.
The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n Examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, and n-decyl group.

  The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.

The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When it has a halogen atom as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ become a haloalkyl group, and when it has an aryl group as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ become an aralkyl group.
As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are illustrated, Among these, a fluorine atom or a chlorine atom is preferable.
Moreover, as said aryl group, a C6-C20 aryl group is preferable and a C6-C12 aryl group is more preferable. Specifically, a phenyl group, an α-methylphenyl group, a naphthyl group and the like can be exemplified, and as an entire alkyl group substituted with an aryl group, that is, as an aralkyl group, a benzyl group, an α-methylbenzyl group, a phenethyl group, A naphthylmethyl group etc. can be illustrated.
As said alkoxy group, a C1-C6 alkoxy group is preferable, a C1-C4 alkoxy group is more preferable, and a methoxy group or an ethoxy group is still more preferable.
Further, when the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group is linear Or a branched alkyl group, it may have a branched alkyl group having 3 to 12 carbon atoms.
These substituents may be further substituted with the above substituents.

In the above formula a1-Z, when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an aryl group, the aryl group preferably has 6 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms. The aryl group may have a substituent, and preferred examples of the substituent include an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a 1-naphthyl group.

R ¹⁰¹ , R ¹⁰² and R ¹⁰³ can be bonded to each other to form a ring together with the carbon atom or oxygen atom to which they are bonded. Examples of the ring structure when R ¹⁰¹ and R ¹⁰² , R ¹⁰¹ and R ^103, or R ¹⁰² and R ¹⁰³ are combined include, for example, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, an adamantane ring and the like. Examples include cyclic cycloalkane rings; ether rings (cyclic ethers) such as tetrahydrofuran ring and tetrahydropyranyl ring.

In Formula a1-Z, it is preferable that any one of R ¹⁰¹ and R ¹⁰² is a hydrogen atom.

(First preferred embodiment)
A first preferred embodiment of the structural unit a1-A having a protected carboxyl group protected by the acid-decomposable group is a structural unit represented by the following formula.

In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least ^one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is an alkyl group or Represents an aryl group, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group;

When R ¹ and R ² are alkyl groups, an alkyl group having 1 to 10 carbon atoms is preferable. When R ¹ and R ² are aryl groups, a phenyl group is preferred. R ¹ and R ² are preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ³ is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
X is preferably a single bond.

(Second preferred embodiment)
Among the first preferred embodiments of the structural unit a1-A having a protected carboxyl group protected by the acid-decomposable group, a more preferred embodiment (second preferred embodiment) is a structural unit represented by the following formula. is there.

In the formula, R ¹²¹ represents a hydrogen atom or a methyl group. L ¹ represents a carbonyl group. R ^{122 to} R ¹²⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and preferably a hydrogen atom.

(Concrete example)
Preferable specific examples of the structural unit a1-A having the protected carboxyl group include the following structural units. R represents a hydrogen atom or a methyl group.

(Polymerizable monomer)
As the polymerizable monomer (radical polymerizable monomer) used for forming the structural unit having a protected carboxyl group represented by the formula a1-Z, a commercially available one may be used, What was synthesize | combined by the method can also be used. For example, it can be synthesized by a synthesis method described in paragraphs 0037 to 0040 of JP2011-221494A.

<< Structural Unit a1-B Having Protected Phenolic Hydroxyl Group >>
The structural unit a1-B having a protected phenolic hydroxyl group is a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group of the structural unit having a phenolic hydroxyl group is protected by the acid-decomposable group described above.
There is no restriction | limiting in particular as a structural unit which has the said phenolic hydroxyl group which can be used for the structural unit a1-B which has the said protected phenolic hydroxyl group, A well-known structural unit can be used. For example, a structural unit derived from hydroxystyrene or α-methylhydroxystyrene is preferable from the viewpoint of sensitivity.
Moreover, as a structural unit having a phenolic hydroxyl group, the structural units described in paragraphs 0065 to 0073 of JP-A-2014-238438 are also preferable from the viewpoint of sensitivity.

Specific examples of the structural unit a1 having a group in which an acid group is protected with an acid-decomposable group are shown below, but the present invention is not limited thereto. Here, R represents a hydrogen atom or a methyl group.
In the present invention, the polymerizable monomer may be modified after polymerization by a polymer reaction or the like. The same applies to the following.

  The molar ratio of the structural unit a to the total structural units constituting the polymer A1-1 is not particularly limited, but is preferably 10 to 100 mol%, and more preferably 20 to 90 mol%.

<Other structural units>
Polymer A1-1 may contain other structural units other than structural unit a1.
Examples of other structural units include a structural unit having a crosslinkable group and a structural unit having a 2-pyrone group. Polymer A1-1 may contain the structural unit which has an acid group mentioned later, and the structural unit p1 mentioned later.

<< Structural Unit Having Crosslinkable Group >>
The polymer A1-1 may contain a structural unit having a crosslinkable group from the viewpoint of curability as long as the effect of the present invention is not impaired. Examples of the crosslinkable group include an epoxy group, an oxetanyl group, —NH—CH ₂ —O—R (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), an ethylenic group, and the like. Examples include a group having a saturated bond and a block isocyanate group, and are represented by an epoxy group, an oxetanyl group, and —NH—CH ₂ —O—R (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). Group, a (meth) acryloyl group, and a block isocyanate group are preferable, and an epoxy group, an oxetanyl group, and —NH—CH ₂ —O—R (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). ) Is more preferable.

(Constitutional unit having epoxy group and / or oxetanyl group)
The polymer A1-1 may contain a structural unit having an epoxy group and / or an oxetanyl group from the viewpoint of curability as long as the effect of the present invention is not impaired. A 3-membered cyclic ether group is also called an epoxy group, and a 4-membered cyclic ether group is also called an oxetanyl group.
The structural unit having an epoxy group and / or oxetanyl group may have at least one of an epoxy group and an oxetanyl group in one structural unit, and one or more epoxy groups and one or more oxetanyl groups, 2 It may have one or more epoxy groups, or two or more oxetanyl groups, may have a total of 1 to 3 epoxy groups and / or oxetanyl groups, and has an epoxy group and / or oxetanyl group. It may have 1 or 2 in total, and may have one epoxy group or one oxetanyl group.

Specific examples of the polymerizable monomer having an epoxy group (radical polymerizable monomer) used for forming a structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, and α-ethylacrylic. Glycidyl acid, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexyl acrylate Methyl, methacrylic acid-3,4-epoxycyclohexylmethyl, α-ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, patent number Paragraph 0 of Japanese Patent No. 4168443 31-0035 such compounds containing an alicyclic epoxy skeleton described in.
Specific examples of the polymerizable monomer (radical polymerizable monomer) used for forming the structural unit having an oxetanyl group include, for example, oxetanyl described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. And (meth) acrylic acid ester having a group.
The polymerizable monomer (radical polymerizable monomer) used to form the structural unit having the epoxy group and / or oxetanyl group contains a monomer containing a methacrylic acid ester structure and an acrylic acid ester structure. It may be a monomer.

  Among these, preferred are glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, (3-ethyloxetane-3-yl) methyl acrylate, and methacrylic acid ( 3-ethyloxetane-3-yl) methyl. These monomers may be used alone or in combination of two or more.

  Preferable specific examples of the structural unit having an epoxy group and / or oxetanyl group include the following structural units. R represents a hydrogen atom or a methyl group.

<< Constitutional Unit Having 2-Pyrone Group >>
As a structural unit which has 2-pyrone group, the structural unit represented by a following formula (P) is mentioned, for example.

Here, in the above formula (P), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² represents a hydrogen atom or a methyl group, L ¹ represents a single bond, having from 1 to 6 carbon atoms Represents an alkylene group or a phenylenemethylene group, and n represents 0 or 1.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹ in the above formula (P) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a tert-butyl group. The group is preferably an ethyl group, and more preferably a methyl group.
Examples of the alkylene group having 1 to 6 carbon atoms represented by L ¹ in the above formula (P) include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, a pentylene group, and a hexylene group. A methylene group, an ethylene group or a propylene group is preferred, and an ethylene group or a propylene group is more preferred.
The phenylenemethylene group represented by L ¹ in the above formula (I) represents divalent —C ₆ H ₄ CH ₂ —.

Specific examples of the structural unit represented by the above formula (P) include, for example, structural units represented by the following formulas (Pa) to (Pe). In each formula, R ² represents a hydrogen atom or a methyl group.

  In addition, the polymer A1-1 is, for example, styrene, methylstyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, from the viewpoint of curability, as long as the effects of the present invention are not impaired. Methyl vinyl benzoate, ethyl vinyl benzoate, 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) Isopropyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate Etc. It may contain a constitutional unit that. Moreover, the structural unit derived from the compound as described in Paragraph 0021-0024 of Unexamined-Japanese-Patent No. 2004-264623 may be included.

  The other structural unit is preferably a structural unit derived from a (meth) acrylic acid alkyl ester, from the viewpoint of adhesion, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, N-butyl (meth) acrylate etc. are mentioned, It is more preferable that it is a structural unit derived from methyl (meth) acrylate. In all the structural units constituting the polymer A1-1, the content of other structural units is preferably 80 mol% or less, preferably 70 mol% or less, and more preferably 60 mol% or less. The lower limit is not particularly limited and is 0 mol%, but may be, for example, 1 mol% or more, or 5 mol% or more.

<Structural unit p1>
Next, the structural unit p1 will be described.
As described above, the polymer component A1 includes the structural unit p1 represented by the following general formula (I), (II), or (III). The polymer component A1 may contain the structural unit p1 as the polymer A1-1, and when it contains the other polymer A1-2, it contains the structural unit p1 as the other polymer A1-2. Also good.

In general formulas (I) to (III), R represents a hydrogen atom or an acid-decomposable group, and R ¹ and R ² each independently represent a hydrogen atom or an alkyl group (preferably having a carbon number of 1 to 12), an alkenyl group (preferably having 1 to 12 carbon atoms), an alkynyl group (preferably having 1 to 12 carbon atoms), an aryl group (preferably having 6 to 18 carbon atoms) or a halogen atom (for example, a fluorine atom, Chlorine atom, bromine atom, iodine atom), and R ¹ and R ² may be bonded to each other to form an alicyclic ring, aromatic ring or heterocyclic ring. Also good. R ³ and R ⁶ are each independently an alkylene group (preferably having a carbon number of 1 to 12), an arylene group (preferably having a carbon number of 6 to 18) or a phenylene alkylene group (—C ₆ H ₆ —R—: R represents an alkylene group (preferably having a carbon number of 1 to 12), R ⁴ and R ⁷ each independently represent a hydrogen atom or a methyl group, and n represents an integer of 0 or 1. In general formula (II), R ⁵ is an alkyl group (preferably having 1 to 12 carbon atoms), an alkenyl group (preferably having 1 to 12 carbon atoms), an aryl group (preferably having 6 to 18 carbon atoms), A phenylalkyl group (—C ₆ H ₆ —R—: R is an alkyl group (preferably having 1 to 12 carbon atoms)) or a phenylalkenyl group (—C ₆ H ₆ —R—: R is an alkenyl group (preferably, Represents a carbon number of 1 to 12)).

The embodiments in which R in general formulas (I) to (III) is an acid-decomposable group are respectively carboxyl groups (—COOR: R in the embodiment in which R in general formulas (I) to (III) is a hydrogen atom. Corresponds to an embodiment in which a hydrogen atom) is protected with an acid-decomposable group.
Specific examples and preferred embodiments of the acid-decomposable group are the same as the above-mentioned “acid-decomposable group that can be used for the structural unit a1-A having a protected carboxyl group”.
When R is an acid-decomposable group, it is preferable to remove the oxygen atom at the bonding position from the group represented by the above-mentioned formula a1-Z. That is, when R is an acid-decomposable group, a preferred embodiment of -OR in (I) to (III) is a group represented by the above-described formula a1-Z.
In the case where R is an acid-decomposable group, the structural unit p1 also corresponds to the above-described “structural unit a1 having a group in which an acid group is protected by an acid-decomposable group”, and in this case, the structural unit p1 Also serves as the structural unit a1.
For example, the first structural unit from the left of A1-1-1 used in the examples described later is an embodiment in which R in the general formula (I) is an acid-decomposable group. The first structural unit from the left of 1 serves both as the structural unit p1 and the structural unit a1. That is, A1-1-1 includes the structural unit p1 and also corresponds to the polymer A1-1 including the above-described structural unit a1.

As described above, R ¹ and R ² may be bonded to each other to form an alicyclic ring, an aromatic ring or a heterocyclic ring. In the case of an alicyclic ring, it may have an unsaturated bond. The ring may have a substituent such as an alkyl group, an alkenyl group, an alkynyl group.
The alicyclic ring may be monocyclic or polycyclic. The number of carbon atoms is preferably 3-12. Examples of the monocyclic alicyclic ring include a cyclopentane ring, a cyclohexane ring, and a cyclooctane ring. Examples of the polycyclic alicyclic ring include a norbornane ring, a tricyclodecane ring, a tetracyclodecane ring, a tetracyclododecane ring, and an adamantane ring. The alicyclic ring may have an unsaturated bond. Examples of the alicyclic ring having an unsaturated bond include a cyclopentene ring, a cyclohexene ring, and a norbornene ring.
It is preferable that carbon number of an aromatic ring is 6-18. Examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring.
The hetero ring is a ring having a hetero atom (for example, alicyclic ring, aromatic ring), and preferably has 1 to 10 carbon atoms. The hetero atom is not particularly limited, and examples thereof include an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom.
For example, the first and second structural units from the left of A1-1-4 used in the examples described later correspond to embodiments in which R ¹ and R ² are bonded to each other to form an alicyclic ring. . The first and second structural units from the left of A1-1-8 correspond to an embodiment in which R ¹ and R ² are bonded to each other to form an alicyclic ring having an unsaturated bond. The first and second structural units from the left of A1-1-5 correspond to embodiments in which R ¹ and R ² are bonded to each other to form an aromatic ring.

<Preferred embodiment>
The polymer A1-1 preferably includes the structural unit p1 described above together with the structural unit a1, and the structural unit p1 corresponding to the structural unit a1 (R in the general formulas (I) to (III) is an acid-decomposable group). A certain embodiment) (hereinafter also referred to as “structural unit ap1”) is more preferable, and the structural unit ap1 other than the structural unit ap1 together with the structural unit ap1 (R in the general formulas (I) to (III) is a “hydrogen atom”. It is more preferable to include an embodiment of Hereinafter, it is also referred to as a polymer AP1 containing the structural unit ap1.
Although the molar ratio of the structural unit ap1 to the total structural units constituting the polymer A1-1 is not particularly limited, it is preferably 10 to 50 mol%.
Although the molar ratio of the structural unit p1 other than the structural unit ap1 with respect to all the structural units constituting the polymer A1-1 is not particularly limited, it is preferably 1 to 20 mol%.

<Molecular weight>
The molecular weight of the polymer contained in the polymer component A1 is a weight average molecular weight in terms of polystyrene, preferably 1,000 to 200,000, more preferably 2,000 to 50,000, and still more preferably 10,000 to 20. , 000. Various characteristics are favorable in the range of said numerical value. The ratio of the number average molecular weight Mn to the weight average molecular weight Mw (dispersity, Mw / Mn) is preferably 1.0 to 5.0, and more preferably 1.5 to 3.5.
In addition, it is preferable to measure the weight average molecular weight and the number average molecular weight in the present invention by a gel permeation chromatography (GPC) method. The measurement by the gel permeation chromatography method in the present invention uses HLC-8020GPC (manufactured by Tosoh Corporation), and TSKgel Super HZ M-H, TSK gel Super HZ4000, TSKgel SuperHZ200 (manufactured by Tosoh Corporation), 4.6 mmID. It is preferable to use THF (tetrahydrofuran) as an eluent.

<Preparation method>
Various methods for synthesizing the polymer in the polymer component A1 are known. To give an example, radical polymerization including a radically polymerizable monomer used to form each of the above-mentioned structural units. It can synthesize | combine by superposing | polymerizing a monomer mixture in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.

<Content>
Although content in particular of polymer component A1 is not restrict | limited, It is preferable that it is 20-99 mass% with respect to the total solid of a composition, and it is more preferable that it is 50-98 mass%. When the content is within this range, an organic film having good curability can be obtained.
The content of the polymer A1-1 in the polymer component A1 is not particularly limited, but is preferably 50 to 100% by mass.

[Photoacid generator B1]
The first aspect of the present invention contains a photoacid generator B1.
The photoacid generator B1 is preferably a compound that reacts with an actinic ray having a wavelength of 300 nm or more, preferably 300 to 450 nm and generates an acid, but is not limited to its chemical structure. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination. The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and an acid of 2 or less. Most preferred are photoacid generators that generate In the present invention, pKa refers to pKa in water at 25 ° C. Those that cannot be measured in water refer to those measured after changing to a solvent suitable for measurement. Specifically, the pKa described in the chemical handbook can be referred to. The acid having a pKa of 3 or less is preferably sulfonic acid or phosphonic acid, and more preferably sulfonic acid.

  Specifically, for example, the photoacid generator described in paragraphs 0067 to 0086 of International Publication No. 2014/066935 can be used as the photoacid generator B1.

  These photoacid generators can be used alone or in combination of two or more.

  Although content in particular of photo-acid generator B1 is not restrict | limited, It is preferable that it is 0.1-10 mass% with respect to the total solid of a composition, and it is more preferable that it is 0.5-5 mass%. . By making content of photo-acid generator B1 into the said range, the solvent resistance of a cured film becomes more favorable.

[Solvent C]
The first aspect of the present invention contains the solvent C.
The solvent C is not particularly limited, and a known solvent can be used. In addition, it is preferable that the photosensitive resin composition of this invention is prepared as a solution which melt | dissolved the component mentioned above and the arbitrary component mentioned later in the solvent. Moreover, as a solvent, the thing which melt | dissolves an essential component and an arbitrary component and does not react with each component is preferable.

  As an example of the solvent C, specifically, for example, the solvents described in paragraphs 0087 to 0090 of International Publication No. 2014/066935 can be used.

  Although content in particular of the solvent C is not restrict | limited, It is preferable that it is 50-95 mass% in a composition, and it is more preferable that it is 70-90 mass%.

[Basic Compound D]
The first aspect of the present invention may contain a basic compound. The basic compound can be arbitrarily selected from those used in chemically amplified positive resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include compounds described in paragraph numbers 0204 to 0207 of JP2011-221494A.

  As an example of the basic compound, specifically, for example, the basic compound described in paragraphs 0116 to 0118 of International Publication No. 2014/066935 can be used.

[Adhesion improver E]
The first aspect of the present invention may contain an adhesion improving agent. Examples of the adhesion improving agent include alkoxysilane compounds.
Although content in particular of an adhesion improving agent is not restrict | limited, It is preferable that it is 0.001-15 mass% with respect to the total solid of a composition, and it is more preferable that it is 0.005-10 mass%.
Only one type of adhesion improver may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

  Specific examples of the adhesion improver include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, β- (3 4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrimethoxysilane and the like. Of these, γ-glycidoxypropyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane are preferable, and γ-glycidoxypropyltrimethoxysilane is more preferable. These can be used alone or in combination of two or more.

[Sensitizer]
The first aspect of the present invention may contain a sensitizer. The sensitizer absorbs actinic rays and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid. For this reason, decomposition | disassembly of a photo-acid generator can be accelerated | stimulated by containing a sensitizer. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in the wavelength range of 350 to 450 nm.

  As an example of a sensitizer, specifically, for example, the sensitizer described in paragraphs 0104 to 0106 of International Publication No. 2014/066935 can be used.

[Surfactant]
The first aspect of the present invention may contain a surfactant. As the surfactant, any of anionic, cationic, nonionic, or amphoteric can be used, but a preferred surfactant is a nonionic surfactant. As the surfactant, for example, those described in paragraph Nos. 0201 to 0205 in JP2012-88459A and those described in paragraph Nos. 0185 to 0188 in JP2011-215580A can be used.

  As an example of surfactant, specifically, for example, surfactants described in paragraphs 0119 to 0123 of International Publication No. 2014/066935 can be used.

[Other ingredients]
In the first aspect of the present invention, known additives such as a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, an organic or inorganic precipitation inhibitor are independently added as necessary. 1 type (s) or 2 or more types can be added.

[Second embodiment of the present invention]
Next, the 2nd aspect of the photosensitive resin composition of this invention is demonstrated.
The photosensitive resin composition according to the second aspect of the present invention contains a polymer component A2 containing a polymer A2-1 containing a structural unit a2 having an acid group, a quinonediazide compound B2, and a solvent C. . Here, the polymer component A2 includes a structural unit p2 represented by the following general formula (IV), (V), or (VI).

[Polymer component A2]
Polymer component A2 is a polymer component containing polymer A2-1 containing structural unit a2 which has an acid group. Moreover, polymer component A2 contains the structural unit p2 represented by general formula (IV), (V), or (VI) mentioned later.

  The polymer component A2 includes other polymer A2-2 added as necessary in addition to the polymer A2-1. The polymer component A2 may contain two or more kinds of polymers A2-1, and may contain two or more kinds of polymers A2-2 when containing the polymer A2-2. .

  The polymer A2-2 that may be contained in the polymer component A2 is not particularly limited as long as it does not include the “structural unit a2 having an acid group”. For example, the “other structural unit” described above ( And a polymer including a structural unit having an acid group).

<Structural unit a2>
The structural unit a2 is a structural unit having an acid group.
The “acid group” in the second aspect of the present invention is incorporated into a polymer as a structural unit having an acid group using a monomer capable of forming an acid group. By including the structural unit a2 having an acid group in the polymer component A2, a highly sensitive photosensitive resin composition can be obtained.
A well-known thing can be used as an acid group, and it does not specifically limit. Specific acid groups include those derived from carboxylic acid groups, those derived from sulfonamide groups, those derived from phosphonic acid groups, those derived from sulfonic acid groups, those derived from phenolic hydroxyl groups, sulfonamide groups And sulfonylimide groups are exemplified, and those derived from carboxylic acid groups and / or those derived from phenolic hydroxyl groups are preferred. In particular, the structural unit having an acid group used in the present invention is preferably a structural unit having a carboxyl group and / or a phenolic hydroxyl group.
The structural unit having an acid group used in the second aspect of the present invention includes a structural unit derived from styrene, a structural unit derived from a vinyl compound, and a structural unit derived from (meth) acrylic acid and / or an ester thereof. preferable. For example, the compounds described in JP-A-2012-88459, paragraph numbers 0021 to 0023 and paragraph numbers 0029 to 0044 can be used. Of these, structural units derived from p-hydroxystyrene, (meth) acrylic acid, maleic acid, and maleic anhydride are preferred.
In the 2nd aspect of this invention, it is more preferable from a viewpoint of a sensitivity to contain the structural unit which has a carboxyl group, or the structural unit which has a phenolic hydroxyl group especially. For example, structural units having acidity described in paragraphs 0021 to 0023 and paragraphs 0029 to 0044 of JP 2012-88459 A can be used.

  The structural unit p2 described later also corresponds to the “structural unit a2 having an acid group”. Therefore, the polymer having the structural unit p2 corresponds to the polymer A2-1.

<Other structural units>
Polymer A2-1 may contain other structural units other than structural unit a2. Specific examples and preferred embodiments of other structural units are the same as those of the first embodiment of the present invention described above.

<Structural unit p2>
Next, the structural unit p2 will be described.
As described above, the polymer component A2 includes the structural unit p2 represented by the general formulas (IV) to (VI). In the general formulas (IV) to (VI), R in the above general formulas (I) to (III) corresponds to an aspect in which a hydrogen atom is present.

In the general formulas (IV) to (VI), R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a halogen atom, and R ⁸ and R ⁹ are bonded to each other. Thus, an alicyclic ring, an aromatic ring, or a heterocyclic ring may be formed. R ¹⁰ and R ¹³ each independently represents an alkylene group, an arylene group or a phenylene alkylene group, R ¹¹ and R ¹⁴ each independently represent a hydrogen atom or a methyl group, and n represents an integer of 0 or 1 Represent. In the general formula (V), R ¹² represents an alkyl group, an alkenyl group, an aryl group, a phenyl group or a phenyl alkenyl group.

Specific examples and preferred embodiments of R ^{8 to} R ¹⁴ are the same as R ^{1 to} R ⁷ in the above general formulas (I) to (III), respectively.

<Preferred embodiment>
It is preferable that polymer A2-1 contains the structural unit p2 mentioned above as the structural unit a2. Hereinafter, the polymer containing the structural unit p2 described above as the structural unit a2 is also referred to as “polymer AP2”.
Although the molar ratio of the structural unit p2 with respect to all the structural units constituting the polymer A2-1 is not particularly limited, it is preferably 10 to 50 mol%.

<Molecular weight>
The preferred embodiment of the molecular weight of the polymer contained in the polymer component A2 is the same as the polymer A2 in the first embodiment of the present invention described above.

<Preparation method>
Specific examples and preferred embodiments of the polymer synthesis method in the polymer component A2 are the same as those of the polymer A2 in the first embodiment of the present invention described above.

<Content>
Although content in particular of polymer component A2 is not restrict | limited, It is preferable that it is 20-99 mass% with respect to the total solid of a composition, and it is more preferable that it is 50-98 mass%. When the content is within this range, an organic film having good curability can be obtained.
The content of the polymer A2-1 in the polymer component A2 is not particularly limited, but is preferably 50 to 100% by mass.

[Quinonediazide compound B2]
The second aspect of the present invention contains a quinonediazide compound B2.
As the quinonediazide compound used in the second embodiment of the present invention, a 1,2-quinonediazide compound that generates a carboxylic acid upon irradiation with actinic rays can be used. As the 1,2-quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound and 1,2-naphthoquinonediazidesulfonic acid halide can be used. As specific examples of these compounds, for example, descriptions in paragraph numbers 0075 to 0078 of JP2012-088459A can be referred to.

  As an example of the quinonediazide compound B2, specifically, for example, a quinonediazide compound described in paragraphs 0133 to 0136 of International Publication No. 2014/066935 can be used.

  These quinonediazide compounds can be used alone or in combination of two or more.

Although content in particular of quinonediazide compound B2 is not restrict | limited, It is preferable that it is 1-50 mass% with respect to the total solid of a composition, and it is more preferable that it is 10-35 mass%.
By setting the content of the quinonediazide compound B2 in the above range, the difference in solubility between the irradiated portion of the actinic ray and the unirradiated portion in the alkaline aqueous solution serving as the developer is large, the patterning performance is improved, and the obtained cured film The solvent resistance becomes better.

[Solvent C]
The second aspect of the present invention contains the solvent C.
The solvent C contained in the second aspect of the present invention is the same as that described above for the solvent in the first aspect of the present invention.

  Although content in particular of the solvent C is not restrict | limited, It is preferable that it is 50-95 mass% in a composition, and it is more preferable that it is 70-90 mass%.

[Other ingredients]
As in the first aspect of the present invention described above, the second aspect of the present invention is an adhesion improving agent, a sensitizer, a basic compound, a surfactant, a thermal radical generator, and a thermal acid generator as necessary. One or more known additives such as an agent, an ultraviolet absorber, a thickener, and an organic or inorganic suspending agent can be added independently.

[Method for Preparing Photosensitive Resin Composition]
The photosensitive resin composition according to the first aspect and the second aspect of the present invention (hereinafter collectively referred to simply as the “photosensitive resin composition of the present invention”) has each component in a predetermined ratio. In addition, it can be prepared by mixing by any method and dissolving by stirring. For example, the photosensitive resin composition of the present invention can also be prepared by mixing each component with a predetermined ratio after preparing each solution in advance in a solvent. The composition solution prepared as described above can be used after being filtered using, for example, a filter having a pore diameter of 0.3 μm.

[Method for producing cured film]
The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
(1) The process of apply | coating the photosensitive resin composition of this invention containing the solvent C to a board | substrate (application | coating process)
(2) Step of removing solvent C from the applied photosensitive resin composition (solvent removal step)
(3) Step of exposing the photosensitive resin composition from which the solvent C has been removed with actinic rays (exposure step)
(4) Step of developing the exposed photosensitive resin composition with a developer (development step)
(5) A step of heat-treating the developed photosensitive resin composition to obtain a cured film (post-baking step)
Each step will be described below in order.
In the step (1), it is preferable to apply the photosensitive resin composition of the present invention on a substrate to form a wet film containing a solvent.

Before performing step (1), the substrate may be cleaned by alkali cleaning, plasma cleaning, or the like. Further, the substrate surface may be treated with hexamethyldisilazane or the like with respect to the cleaned substrate. The method of treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method of exposing the substrate to hexamethyldisilazane vapor.
Examples of the substrate include an inorganic substrate, a resin substrate, a substrate using a composite material of a resin material and an inorganic material.
Examples of the inorganic substrate include a glass substrate, a quartz substrate, a silicone substrate, a silicon nitride substrate, and a composite substrate obtained by depositing molybdenum, titanium, aluminum, copper, or the like on these substrates.
As the resin substrate, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, Fluorine resin such as polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, Made of synthetic resin such as aromatic ether, maleimide-olefin, cellulose, episulfide compound Plate, and the like.
These substrates may have a multi-layered structure such as a thin film transistor (TFT) element, depending on the form of the final product.
The method for applying the photosensitive resin composition to the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, or the like may be used. it can.
In the case of the slit coating method, the relative moving speed between the substrate and the slit die is preferably 50 to 120 mm / sec.
The wet film thickness when the photosensitive resin composition is applied is not particularly limited, and can be applied with a film thickness according to the application. For example, 0.5-10 micrometers is preferable.
Before applying the photosensitive resin composition of the present invention to the substrate, it is also possible to apply a so-called prewetting method as described in JP-A-2009-145395.

  In the step (2), the solvent is removed from the wet film formed by applying the photosensitive resin composition by vacuum (vacuum) and / or heating to form a dry film on the substrate. The heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are within the above ranges, when performing the step (4) described later, the adhesion of the pattern tends to be better, and the residue tends to be further reduced.

In the step (3), the substrate provided with the dry film is irradiated with actinic rays having a predetermined pattern. In this step, an acid group (such as a carboxyl group or a phenolic hydroxyl group) is generated in the exposed area, and the solubility in the developer in the exposed area is improved.
That is, in an embodiment including a polymer component having a structural unit having a group in which an acid group is protected by an acid-decomposable group, and a photoacid generator, the photoacid generator is decomposed by irradiation with actinic rays. Acid is generated. Then, the acid-decomposable group contained in the dry film is hydrolyzed by the catalytic action of the generated acid to generate a carboxyl group or a phenolic hydroxyl group as the acid group.
Moreover, in the aspect containing a quinone diazide compound, a carboxyl group is produced | generated as an acid group from a quinone diazide compound by irradiation of actinic light.
As a light source of actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generator, etc. can be used, i-line (365 nm), h-line (405 nm), Actinic rays having a wavelength of 300 nm to 450 nm, such as g-line (436 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed. The exposure amount is preferably 1 to 500 mJ / cm ² .
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, a lens scanner, and a laser exposure can be used. In addition, exposure using a so-called super-resolution technique can be performed. Examples of the super-resolution technique include multiple exposure in which exposure is performed a plurality of times, a method using a phase shift mask, and an annular illumination method. By using these super-resolution techniques, it is possible to form a higher definition pattern, which is preferable.

In the step (4), the photosensitive resin composition is developed using a developer. A positive image is formed by removing an exposed area having an acid group (such as a carboxyl group or a phenolic hydroxyl group) that is easily dissolved in the developer.
The developer used in the development step preferably contains an aqueous solution of a basic compound. Examples of basic compounds include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; sodium bicarbonate, potassium bicarbonate Alkali metal bicarbonates such as: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, diethyldimethylammonium hydroxide, and other tetraalkylammonium hydroxides: Alkyl) trialkylammonium hydroxides; silicates such as sodium silicate and sodium metasilicate; ethylamine, propylamine, diethylamine, triethylammonium Alkyl amines such as dimethyl alcohol; alcohol amines such as dimethyl ethanol amine and triethanol amine; 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0 ] Cycloaliphatic amines such as -5-nonene can be used.
Of these, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide) are preferable.
An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 500 seconds, and the development method may be any of a liquid piling method (paddle method), a shower method, a dipping method, and the like.
A rinsing step can also be performed after the developing step. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned. Moreover, the process of exposing the developed said photosensitive resin composition can also be performed after the process of image development and before the process of heat-processing.

In the step (5), the obtained positive image is heated to thermally decompose the acid-decomposable group to generate an acid group (such as a carboxyl group or a phenolic hydroxyl group). A cured film can be formed by crosslinking. This heating is preferably performed using a heating device such as a hot plate or an oven. The heating temperature is preferably 200 ° C to 350 ° C, more preferably 250 ° C to 350 ° C. The heating time is preferably 5 to 90 minutes on a hot plate and 30 to 120 minutes for an oven. By proceeding the cyclization reaction or the crosslinking reaction by heating, a cured film having more excellent heat resistance, hardness and the like can be formed. In addition, when the heat treatment is performed in a nitrogen atmosphere, the transparency can be further improved.
Prior to post-baking, post-baking can be performed after baking at a relatively low temperature (addition of a middle baking process). When performing middle baking, it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Moreover, middle baking and post-baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
Prior to post-baking, the entire surface of the patterned substrate was re-exposed with actinic rays (post-exposure), and then post-baked to generate an acid from the photoacid generator present in the unexposed portion, thereby performing a crosslinking step. It can function as a catalyst to promote, and can accelerate the curing reaction of the film. As a preferable exposure amount when the post-exposure step is included, 100 to 3,000 mJ / cm ² is preferable, and 100 to 500 mJ / cm ² is particularly preferable.

  The cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist. When a cured film obtained by heat treatment in the post-bake process is used as a dry etching resist, dry etching processes such as ashing, plasma etching, and ozone etching can be performed as the etching process.

  Moreover, the manufacturing method of the cured film of this invention may perform a photo-alignment process from a viewpoint of functioning the obtained cured film as an alignment film after the said post-baking process.

  The photo-alignment treatment is not particularly limited except that light having a wavelength of 313 nm or less is used, but it is preferable to use polarized ultraviolet rays for obtaining uniform alignment. In this case, the method of irradiating polarized ultraviolet rays is not particularly limited. In addition, there is no restriction | limiting in particular as polarized light, For example, linearly polarized light, circularly polarized light, elliptically polarized light etc. are mentioned, Among these, linearly polarized light is preferable.

  Moreover, it is only necessary to obtain substantially polarized light, and non-polarized light may be irradiated at an angle inclined from the normal line of the thin film. In other words, non-polarized light may be irradiated from an oblique direction on the surface of the cured film. “Inclined irradiation” is not particularly limited as long as it is a direction inclined by a polar angle θ (0 <θ <90 °) with respect to the normal direction of the surface of the cured film, and can be appropriately selected according to the purpose. However, θ is preferably 20 to 80 °.

Examples of the light source used include a xenon lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, and a metal halide lamp.
By using an interference filter, a color filter, or the like with respect to ultraviolet rays obtained from such a light source, the wavelength range of irradiation can be limited. Further, linearly polarized light can be obtained by using a polarizing filter or a polarizing prism for the light from these light sources.

[Curing film]
The cured film of the present invention is a cured film formed by curing the above-described photosensitive resin composition of the present invention. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the manufacturing method of the cured film of this invention mentioned above.
The cured film of the present invention can be suitably used as an interlayer insulating film, a protective film, and a planarizing film.
The photosensitive resin composition of the present invention can provide an interlayer insulating film having high transparency even when baked at a high temperature. The interlayer insulation film formed using the photosensitive resin composition of the present invention has high transparency and is useful for applications such as a liquid crystal display device, an organic electroluminescence display device, and a touch panel.

[Polymerizable monomer]
The polymerizable monomer (polymerizable monomer p) of the present invention is represented by the following general formula (VII) or (VIII). The polymerizable monomer is suitably used for the synthesis of the polymer having the structural unit p1 and the structural unit p2.

In the general formulas (VII) and (VIII), R represents a group that forms an acetal group together with the oxygen atom to which R is bonded, and R ¹ and R ² are each independently a hydrogen atom, an alkyl group, an alkenyl group, An alkynyl group, an aryl group or a halogen atom, and R ¹ and R ² may be bonded to each other to form an alicyclic ring, an aromatic ring or a heterocyclic ring; Good. R ³ and R ⁶ each independently represents an alkylene group, an arylene group or a phenylene alkylene group, R ⁴ and R ⁷ each independently represent a hydrogen atom or a methyl group, and n is an integer of 0 or 1 Represents.

  R is preferably one obtained by removing the oxygen atom at the bonding position from the group represented by the formula a1-Z. That is, -OR is preferably a group represented by the above-described formula a1-Z.

Specific examples and preferred embodiments of R ¹ to R ⁴ and ^R 6 to R ⁷ are respectively the same as ^R 1 to R ⁴ and ^R 6 to R ⁷ in general formula (I) ~ (III) .

[Polymer]
The polymer (polymer P) of the present invention is a polymer containing the structural unit represented by the general formula (I) or (III) described above. Here, R in the general formula (I) or (III) is preferably a group that forms an acetal group together with the oxygen atom to which R is bonded, and is bonded from the group represented by the above-described formula a1-Z. More preferably, the oxygen atom at the position is removed. That is, -OR is more preferably a group represented by the above-described formula a1-Z.

  Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples. Unless otherwise specified, “part” and “%” are based on mass.

<Synthesis of polymer (A)>
(Synthesis Example 1: Synthesis of A1-1-1)
The following A1-1-1 was synthesized as follows. Here, the parentheses indicate the molar ratio.

NMP (8.30 g) was heated and stirred at 70 ° C. under a nitrogen stream.
Subsequently, monomer a1-9 (4.25 g (corresponding to 35 mol% in all monomer components)), a2-1 (0.47 g (corresponding to 5 mol% in all monomer components)), MMA (methacrylic acid) Acid mixture) (2.40 g (corresponding to 60 mol% in all monomer components)), radical polymerization initiator V-65 (0.47 g), and NMP (8.30 g) over 2 hours. Then, the mixture was further reacted at 70 ° C. for 2 hours to obtain a solution of polymer A1-1-1 (solid content concentration: 30%).
The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the obtained polymer A1-1-1 was 8,800.

Monomer a2-1 was synthesized as follows.
4-vinylbenzylamine (manufactured by Tokyo Chemical Industry Co., Ltd., 10.0 g, 0.075 mol) was dissolved in THF (50 mL), and succinic anhydride (manufactured by Wako Pure Chemical Industries, Ltd., 7. 51 g, 0.075 mol) was added. After raising the temperature to room temperature and stirring for 4 hours, ethyl acetate was added to reslurry, filtered and dried to obtain 16.1 g of a2-1 (yield 92%).
Monomer a1-9 was synthesized as follows.
a2-1 (10.0 g, 0.043 mol) and 2,3-dihydrofuran (manufactured by Kawaken Fine Chemical Co., Ltd., 50 g) were mixed, heated and stirred at 50 ° C. for 6 hours, then allowed to cool and concentrated under reduced pressure. The precipitated crystals were reslurried with hexane / ethyl acetate to obtain 11.8 g (yield 90.7%) of monomer a1-9.

(Synthesis Example 2: Synthesis of A1-1-7)
The following A1-1-7 was synthesized as follows. Here, the parentheses indicate the molar ratio.

NMP (13.87 g) was heated and stirred at 90 ° C. under a nitrogen stream.
Subsequently, 4-vinylbenzylamine (6.99 g (corresponding to 40 mol% in all monomer components)), MMA (2.25 g (corresponding to 60 mol% in all monomer components)), radical polymerization initiator A mixed solution of V-601 (0.65 g) and NMP (13.87 g) was added dropwise over 2 hours, and the mixture was further reacted at 90 ° C. for 2 hours to obtain an intermediate A1-1 of polymer A1-1-7. A -7B solution was obtained.
To the obtained solution of A1-1-7B, maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd., 5.15 g, 0.053 mol) was added and stirred for 1 hour. The reaction solution was poured into distilled water (150 mL), and the precipitated crystals were filtered and dried to obtain an intermediate A1-1-7A of A1-1-7.
The obtained A1-1-7A and 2,3-dihydrofuran (manufactured by Kawaken Fine Chemical Co., Ltd., 74 g) were mixed, heated to 50 ° C., and reacted for 6 hours. The obtained A1-1-7 solution was concentrated under reduced pressure, and the precipitated solid was redissolved in NMP to obtain a 25% by mass solution.
The obtained polymer A1-1-7 had a weight average molecular weight (Mw) of 9000 as measured by gel permeation chromatography (GPC).

(Synthesis Example 3: Synthesis of A1-1-15)
The following A1-1-15 was synthesized as follows. Here, the parentheses indicate the molar ratio.

In the same manner as A1-1-1, monomer a1-7 (corresponding to 35 mol% in all monomer components), a2-2 (corresponding to 5 mol% in all monomer components), MMA (total single amount) A1-1-15 was synthesized by copolymerization of 60 mol% in the body component.
The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the obtained polymer A1-1-15 was 9,600.

  In addition, operation similar to the said synthesis example was performed, and the other polymer was also synthesize | combined among the polymers (A) mentioned later.

<Preparation of photosensitive resin composition>
Each component shown in Table 1 was blended in the addition amount (parts by mass) shown in Table 1 and stirred. And the photosensitive resin composition of each Example and a comparative example was prepared by filtering with the filter made from a polytetrafluoroethylene with a hole diameter of 0.3 micrometer.

<Evaluation of sensitivity>
Each photosensitive resin composition was slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (Corning)), then pre-baked on a hot plate at 90 ° C. for 120 seconds to evaporate the solvent, and the thickness 3 A photosensitive resin composition layer having a thickness of 0.0 μm was formed.
Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using a high-pressure mercury lamp (proxy exposure machine). The exposed photosensitive resin composition layer was developed with an alkali developer (0.7 mass% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
The sensitivity was the optimum i-line exposure (Eopt) when resolving a 10 μm contact hole pattern by these operations. The results are shown in Table 1. The evaluation criteria are as follows. From the viewpoint of sensitivity, 2 or more is preferable, and 3 or more is particularly preferable.
4: 40mJ / cm ² less than 3: 40mJ / cm ² or more 80 mJ / cm ² less than ^2: 80mJ / cm 2 or more 200 mJ / cm ² less than 1: 200mJ / cm ² or more (when it is not possible to form a pattern, even 200 mJ / cm ² or more including)

<Evaluation of corrosion resistance (wet heat resistance)>
Each photosensitive resin composition was spin-coated on a glass substrate with a laminated sputtering film of titanium / aluminum, and then pre-baked on a hot plate at 90 ° C. for 120 seconds to form a photosensitive resin composition layer having a thickness of 3 μm. Next, the cured film was produced by heating at 230 degreeC for 1 hour in oven. This cured film was tested for 18 hours at 60 ° C. and 90% humidity, and then the degree of discoloration of the substrate surface was evaluated. A titanium / aluminum laminated sputtered glass substrate with no cured film was also tested at the same time, and the following criteria were used as the criteria for the degree of discoloration. The results are shown in Table 1. From the viewpoint of corrosion resistance, 3 or more is preferable.
4: No discoloration was observed on the titanium surface under the cured film after the test.
3: Discoloration was observed on the titanium surface under the cured film after the test, but the discolored area of the titanium surface under the cured film was less than 20% of the discolored area when the cured film was not formed.
2: The discolored area of the titanium surface under the cured film was 20% or more and less than 40% of the discolored area when the cured film was not formed.
1: The discolored area of the titanium surface under the cured film was 40% or more of the discolored area when the cured film was not formed.

<Evaluation of low dielectric constant>
Each photosensitive resin composition was diluted 2.5 times with cyclohexanone and spin-coated on a bare wafer (N-type low resistance) (manufactured by SUMCO), and then prebaked at 90 ° C. for 120 seconds to obtain a thickness of 0 A photosensitive resin composition layer having a thickness of 35 μm was formed. Next, the cured film was produced by heating at 230 degreeC for 1 hour in oven. With respect to this cured film, the relative dielectric constant was measured at a measurement frequency of 1 MHz using CVmap92A (made by Four Dimensions Inc.). The results are shown in Table 1. The evaluation criteria are as follows. From the viewpoint of low dielectric constant, 3 or more is preferable.
4: The relative dielectric constant is less than 3.3.
3: The relative dielectric constant is 3.3 or more and less than 3.5.
2: The relative dielectric constant is 3.5 or more and less than 3.8.
1: The relative dielectric constant is 3.8 or more.

  In Table 1, the polymer (A) is as follows. Here, the parentheses indicate the molar ratio.

In Table 1, the photoacid generator (B) is as follows. B3 is a sensitizer.
B1-1: Oxime sulfonate having the following structure: B1-2: Oxime sulfonate having the following structure: B1-3: Oxime sulfonate having the following structure: B1-4: PAG-103 (manufactured by BASF)
・ B3: 9,10-dibutoxyanthracene (manufactured by Kawasaki Industry Co., Ltd.)

In Table 1, the quinonediazide compound (B2) is as follows.
B2-1: 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester

In Table 1, the solvent (C) is as follows.
C-1: MEDG (diethylene glycol ethyl methyl ether, manufactured by Daicel Corporation)
C-2: NMP (N-methylpyrrolidone, manufactured by Wako Pure Chemical Industries, Ltd.)
C-3: PGMEA (propylene glycol 1-monomethyl ether 2-acetate, manufactured by Daicel Corporation)

In Table 1, the basic compound (D) is as follows.
D-1: Compound having the following structure (manufactured by DSP Gokyo Food & Chemical Co., Ltd.)
D-2: 1,5-diazabicyclo [4.3.0] -5-nonene (manufactured by Wako Pure Chemical Industries, Ltd.)
D-3: Triphenylimidazole (manufactured by Tokyo Chemical Industry)

In Table 1, the adhesion improver (E) is as follows.
E-1: KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) (in the structural formula, Me represents a methyl group)

In Table 1, the additive (F) is as follows.
F-1: Irganox 1035 (manufactured by BASF)
・ F-2: Celoxide 2021P (manufactured by Daicel Corporation)
F-3: Duranate 17B-60P (Asahi Kasei Chemicals Corporation)
F-4: Takenate B-870N (Mitsui Chemicals, Inc.)

In Table 1, the surfactants are as follows.
・ W-1: Megafac F554 (manufactured by DIC Corporation, fluorosurfactant)

As can be seen from Table 1 (Part 1), Examples 1 to 40 using the polymer component having the structural unit a1 and the structural unit p1 are high in sensitivity, and the obtained cured film has excellent corrosion resistance and It showed low dielectric constant.
Comparison of Examples 1 to 19 and 22 to 23 (the polymer component A1 does not contain a constituent unit having an acid group other than the constituent unit p1, or the polymer component A1 has an acid group other than the constituent unit p1) In contrast, the structural unit p1 is represented by the general formula (I) from the examples including the structural unit having an epoxy group at a molar ratio equal to or higher than the molar ratio of the structural unit having the acid group. 6, 8-19 and 22-23 showed better corrosion resistance.
Further, from the comparison of Examples 15 and 24-29, Examples 15, 24 and 27 in which the ratio of the polymer AP1 to the total solid content is 80% by mass or more have better corrosion resistance and low dielectric constant. Indicated.

  On the other hand, the cured films obtained from the compositions of Comparative Examples 1 and 2 using the polymer component having no structural unit p1 have insufficient corrosion resistance or low dielectric constant.

Further, as can be seen from Table 1 (No. 2), Examples 41 to 56 using the polymer component having the structural unit a2 and the structural unit p2 have high sensitivity, and the obtained cured film has excellent corrosion. Resistant and low dielectric constant.
Comparison of Examples 41 to 50 and 52 (Polymer component A2 does not include a structural unit having an acid group other than the structural unit p2 or Polymer component A1 includes a structural unit having an acid group other than the structural unit p2) From the aspect including the structural unit having an epoxy group at a molar ratio equal to or higher than the molar ratio of the structural unit having the acid group),
Moreover, contrast of Example 41-43 and 45-51 (The polymeric component A2 contains the structural unit represented by general formula (IV), and does not have the structural unit which has an epoxy group. In contrast, Examples 42 and 45 to 51, in which R ⁸ and R ⁹ in general formula (IV) are bonded to each other to form an alicyclic ring, showed a more excellent low dielectric constant.
Moreover, from the comparison of Example 43 and 53-56, Example 43, 53, and 55 whose ratio of polymer AP2 with respect to the total solid content is 50 mass% or more showed more excellent corrosion resistance.

  On the other hand, the cured films obtained from the compositions of Comparative Examples 5 to 7 using the polymer component having no structural unit p2 have insufficient corrosion resistance or low dielectric constant.

Claims (6)

A polymer component A1 containing a polymer A1-1 containing a structural unit a1 having a group in which an acid group is protected by an acid-decomposable group, a photoacid generator B1, and a solvent C,
The photosensitive resin composition in which the polymer component A1 includes a structural unit p1 represented by the following general formula (I), (II), or (III).

In the general formulas (I) to (III), R represents a hydrogen atom or an acid-decomposable group, and R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl Represents a group or a halogen atom, and R ¹ and R ² may be bonded to each other to form an alicyclic ring, an aromatic ring or a heterocyclic ring, and may have an unsaturated bond in the case of an alicyclic ring. R ³ and R ⁶ each independently represents an alkylene group, an arylene group or a phenylene alkylene group, R ⁴ and R ⁷ each independently represent a hydrogen atom or a methyl group, and n is an integer of 0 or 1 Represents. In general formula (II), R ⁵ represents an alkyl group, an alkenyl group, an aryl group, a phenylalkyl group or a phenylalkenyl group. A polymer component A2 containing a polymer A2-1 containing a structural unit a2 having an acid group, a quinonediazide compound B2, and a solvent C,
The photosensitive resin composition in which the polymer component A2 includes a structural unit p2 represented by the following general formula (IV), (V), or (VI).

In the general formulas (IV) to (VI), R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a halogen atom, and R ⁸ and R ⁹ are bonded to each other. Thus, an alicyclic ring, an aromatic ring, or a heterocyclic ring may be formed. R ¹⁰ and R ¹³ each independently represents an alkylene group, an arylene group or a phenylene alkylene group, R ¹¹ and R ¹⁴ each independently represent a hydrogen atom or a methyl group, and n represents an integer of 0 or 1 Represent. In the general formula (V), R ¹² represents an alkyl group, an alkenyl group, an aryl group, a phenyl group or a phenyl alkenyl group.   The photosensitive resin composition according to claim 1, wherein R in the general formulas (I) to (III) is an acid-decomposable group. Applying the photosensitive resin composition according to any one of claims 1 to 3 to a substrate;
Removing the solvent C from the applied photosensitive resin composition;
Exposing the photosensitive resin composition from which the solvent C has been removed with actinic rays;
Developing the exposed photosensitive resin composition with a developer;
A process for producing a cured film comprising heat-treating the developed photosensitive resin composition to obtain a cured film.   The cured film formed by hardening the photosensitive resin composition of any one of Claims 1-3.   The cured film according to claim 5, which is one type selected from the group consisting of an insulating film, a protective film, and a planarizing film.