JP5867169B2 - Positive photosensitive resin composition, interlayer insulating film for display element and method for forming the same - Google Patents

Description

  The present invention relates to a positive photosensitive resin composition, an interlayer insulating film for display elements, and a method for forming the same.

  The display element is generally provided with a display element interlayer insulating film for the purpose of insulating between wirings arranged in layers. As a material for forming an interlayer insulating film for a display element, a positive photosensitive resin composition is used because the number of steps for obtaining a necessary pattern shape is small and a high level of flatness is required for the obtained interlayer insulating film for a display element. Things are widely used. Such a positive photosensitive resin composition is required to have good sensitivity and storage stability, and an interlayer insulating film for a display element is required to have excellent light resistance, heat resistance and the like in addition to the above flatness.

  As such a positive photosensitive resin composition, an acrylic resin is widely employed, and for example, a composition containing a crosslinking agent, an acid generator and an alkali-soluble resin is known (Japanese Patent Laid-Open No. 2004-2004). No. 4669). The alkali-soluble resin has a protecting group (a group that is insoluble or hardly soluble in an alkaline aqueous solution and can be dissociated by the action of an acid). After the protective group is dissociated by exposure, the alkali aqueous resin is a developer. A resin that becomes soluble. As another positive photosensitive resin composition, there has been proposed a positive photosensitive resin composition containing an acetal structure and / or a ketal structure, a resin containing an epoxy group, and an acid generator (Japanese Patent Application Laid-Open (JP-A)). 2004-264623).

  However, when an attempt is made to form an interlayer insulating film for a display element using a conventional positive photosensitive resin composition, the amount of decrease in the film thickness of the unexposed portion in the development process is large, and the flatness of the interlayer insulating film for the display element Are disadvantageous, and there is a disadvantage that a deviation from the designed film thickness occurs. Moreover, in order to avoid this inconvenience, it is necessary to strictly adjust the development time, which leads to inefficiency of the production process.

  In view of such a situation, a positive photosensitive resin composition having good sensitivity and storage stability, and a display element having a small amount of change in film thickness of an unexposed portion with respect to development time in addition to excellent light resistance and heat resistance. Development of an interlayer insulating film for use is desired.

JP 2004-4669 A JP 2004-264623 A

  The present invention has been made based on the circumstances as described above, and in addition to good sensitivity and storage stability, a positive photosensitive resin composition having a small amount of change in the thickness of an unexposed portion with respect to development time, excellent Another object is to provide an interlayer insulating film for display elements having light resistance and heat resistance, and a method for forming the same.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立して水素原子、アルキル基、シクロアルキル基又はアリール基である。但し、上記アルキル基、シクロアルキル基及びアリール基が有する水素原子の一部又は全部は、置換されていてもよい。また、Ｒ^１及びＲ^２が共に水素原子である場合はない。Ｒ^３は、アルキル基、シクロアルキル基、アラルキル基、アリール基又は−Ｍ（Ｒ^４）_３で表される基である。このＭは、Ｓｉ、Ｇｅ又はＳｎである。Ｒ^４は、それぞれ独立してアルキル基である。また、Ｒ^１とＲ^３とが連結して環状エーテル構造を形成してもよい。但し、Ｒ^３で表されるこれらの基が有する水素原子の一部又は全部は、置換されていてもよい。）

（式（２）中、Ｒ^５は、直鎖状、分岐状若しくは環状のアルキル基又はアリール基である。但し、上記アルキル基及びアリール基が有する水素原子の一部又は全部は、置換されていてもよい。） The invention made to solve the above problems is
[A] a copolymer comprising a structural unit (I) having a group represented by the following formula (1) and a structural unit (II) having one or more (meth) acryloyloxy groups (hereinafter referred to as “[A] Also referred to as "copolymer"),
[B] A compound having an oxime sulfonate group represented by the following formula (2) (hereinafter also referred to as “[B] compound”),
[C] A positive photosensitive resin composition containing a radical scavenger and [D] a solvent.

(In formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, provided that the hydrogen atom of the alkyl group, cycloalkyl group and aryl group is A part or all of them may be substituted, and R ¹ and R ² are not both hydrogen atoms, and R ³ is an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, or —M ( R ⁴ ) is a group represented by _3. M is Si, Ge or Sn, each R ⁴ is independently an alkyl group, and R ¹ and R ³ are linked to form a cyclic group. An ether structure may be formed, provided that a part or all of the hydrogen atoms of these groups represented by R ³ may be substituted.)

(In formula (2), R ⁵ is a linear, branched or cyclic alkyl group or aryl group, provided that part or all of the hydrogen atoms of the alkyl group and aryl group are substituted. May be.)

  The group represented by the above formula (1) in the structural unit (I) exists as a group (acid dissociable group) that dissociates in the presence of an acid to generate a polar group. B] The [A] copolymer which is dissociated by the acid generated from the compound and is consequently insoluble in alkali becomes alkali-soluble. In addition, the [A] copolymer contains the structural unit (II) having the above specific structure, thereby forming a crosslinked structure between the molecular chains. In addition to good sensitivity and storage stability, the unexposed area with respect to the development time. The amount of change in film thickness can be suppressed, and an interlayer insulating film for display elements having excellent light resistance and heat resistance can be formed. Furthermore, the [C] radical scavenger contained in the positive photosensitive resin composition can decompose radicals generated by exposure or heating, or peroxide generated by oxidation, and cleave bond of polymer molecules. It is a component that can be prevented. As a result, the positive photosensitive resin composition can further suppress the change in film thickness.

In the group represented by the above formula (1), it is preferable that R ¹ and R ³ are linked to form a cyclic ether structure. Moreover, it is preferable that group represented by the said Formula (1) is group represented by following formula (1-1).

  By making the group represented by the formula (1) into the specific ring structure, the hydrophobicity becomes higher with respect to the developer, and the film thickness reduction can be further suppressed.

  [A] The content of the structural unit (II) in the copolymer is preferably 5 mol% or more and 60 mol% or less. [A] When the copolymer contains the structural unit (II) at the above-mentioned specific content, the cross-linked structure between the molecular chains is further promoted, and as a result, in addition to better sensitivity and storage stability, the undeveloped relative to the development time. An amount of change in the film thickness of the exposed portion can be further suppressed, and an interlayer insulating film for a display element having more excellent light resistance and heat resistance can be formed.

  The structural unit (II) preferably has two or more (meth) acryloyloxy groups. The structural unit (II) has two or more (meth) acryloyloxy groups, and in addition to better sensitivity and storage stability, the amount of change in the film thickness of the unexposed area with respect to the development time can be further suppressed. The shape stability of the hole can be further improved. In addition, it is possible to form an interlayer insulating film for a display element having excellent light resistance and heat resistance.

  [D] The solvent is preferably at least one solvent selected from the group consisting of ketones, ethylene glycol monoalkyl ethers, diethylene glycol alkyl ethers and propylene glycol monoalkyl ether acetates. By selecting the specific solvent, it is possible to suppress coating unevenness on the coating surface when a large substrate is applied by a spinless method.

  The positive photosensitive resin composition preferably further contains a compound having two or more epoxy groups in the [E] molecule (hereinafter also referred to as “[E] epoxy compound”). When the positive photosensitive resin composition further contains an [E] epoxy compound, the light resistance and heat resistance of the interlayer insulating film for display elements formed from the positive photosensitive resin composition are further improved. be able to.

  The positive photosensitive resin composition is suitable as a material for forming an interlayer insulating film for display elements. Further, the present invention suitably includes an interlayer insulating film for a display element formed from the positive photosensitive resin composition.

The method for forming an interlayer insulating film for a display element according to the present invention includes:
(1) The process of forming the coating film of the said positive type photosensitive resin composition on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) a step of developing the coating film irradiated with the radiation; and (4) a step of heating the developed coating film.

  According to the formation method, an interlayer insulating film for a display element having high contact hole diameter stability in addition to excellent light resistance and heat resistance can be formed. Moreover, since the amount of decrease in the film thickness of the unexposed portion with respect to the development time can be suppressed, the production process margin can be improved as a result, and the yield can be improved. Furthermore, an interlayer insulating film for a display element having a fine and elaborate pattern can be easily formed by forming a pattern by exposure, development and heating utilizing photosensitivity. Therefore, the formed interlayer insulation film for display elements can be used suitably for display elements, such as a liquid crystal display element and an organic EL display element.

  As described above, the positive photosensitive resin composition of the present invention can suppress the change in the film thickness of the unexposed part with respect to the development time, in addition to good sensitivity and storage stability, and has excellent light resistance and heat resistance. An interlayer insulating film for a display element having the above can be provided. In addition, the stability of the contact hole diameter can be improved. Since the film thickness reduction amount can be suppressed, the production process margin can be improved as a result, and the yield can be improved. Furthermore, an interlayer insulating film for a display element having a fine and elaborate pattern can be easily formed by forming a pattern by exposure, development and heating utilizing photosensitivity. Therefore, the formed interlayer insulation film for display elements can be used suitably for display elements, such as a liquid crystal display element and an organic EL display element.

<Positive photosensitive resin composition>
The positive photosensitive resin composition of the present invention contains a [A] copolymer, a [B] compound, a [C] radical scavenger and a [D] solvent. Moreover, the positive photosensitive resin composition may contain an [E] epoxy compound as a suitable component. Furthermore, other optional components may be contained as long as the effects of the present invention are not impaired. Hereinafter, each component will be described in detail.

<[A] Copolymer>
[A] The copolymer is a copolymer comprising a structural unit (I) having a group represented by the above formula (1) and a structural unit (II) having one or more (meth) acryloyloxy groups. . Further, the [A] copolymer may contain other structural units as long as the effects of the present invention are not impaired. In addition, the [A] copolymer may contain 2 or more types of each structural unit. Hereinafter, each structural unit will be described in detail.

[Structural unit (I)]
The structural unit (I) has a group represented by the above formula (1). In said formula (1), R < ¹ > and R < ² > are respectively independently a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. However, one part or all part of the hydrogen atom which the said alkyl group, a cycloalkyl group, and an aryl group have may be substituted. Further, there is no case where R ¹ and R ² are both hydrogen atoms. R ³ is an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, or a group represented by —M (R ⁴ ) ₃ . This M is Si, Ge, or Sn. R ⁴ is each independently an alkyl group. R ¹ and R ³ may be linked to form a cyclic ether structure. However, one part or all part of the hydrogen atom which these groups represented by R < ³ > have may be substituted.

Examples of the alkyl group represented by R ¹ and R ² include linear and branched alkyl groups having 1 to 30 carbon atoms. Examples of the linear and branched alkyl group having 1 to 30 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and an n-octyl group. , N-dodecyl group, n-tetradecyl group, n-octadecyl group and other linear alkyl groups, i-propyl group, i-butyl group, t-butyl group, neopentyl group, 2-hexyl group, 3-hexyl group And a branched alkyl group such as.

Examples of the cycloalkyl group represented by R ¹ and R ² include a cycloalkyl group having 3 to 20 carbon atoms. Moreover, this C3-C20 cycloalkyl group may be polycyclic. Examples of the cycloalkyl group having 3 to 20 carbon atoms include cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl, cyclooctyl, bornyl group, norbornyl group, adamantyl group and the like.

Examples of the aryl group represented by R ¹ and R ² include an aryl group having 6 to 14 carbon atoms. The aryl group having 6 to 14 carbon atoms may be a single ring, a structure in which single rings are connected, or a condensed ring. Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group.

Examples of the optionally substituted alkyl group, cycloalkyl group and aryl group represented by R ¹ and R ² include a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, a cyclo group. An alkyl group (eg, cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl, cyclooctyl, bornyl group, norbornyl group, adamantyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), alkoxy group (eg, methoxy group) , An ethoxy group, a propoxy group, an n-butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group and the like, and an acyl group (for example, an acetyl group and a propionyl group). , Butyryl group, i-butyryl group and the like having 2 to 20 carbon atoms A siloxy group), an acyloxy group (for example, an acetoxy group, an ethylyloxy group, a butyryloxy group, a t-butyryloxy group, a t-amylyloxy group, etc., an acyloxy group having 2 to 10 carbon atoms), an alkoxycarbonyl group (for example, a methoxycarbonyl group) C2-C20 alkoxycarbonyl groups such as ethoxycarbonyl group and propoxycarbonyl group), haloalkyl groups (for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group) , N-octyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group and the like linear alkyl group, i-propyl group, i-butyl group, t-butyl group, neopentyl group, 2-hexyl group Alkyl groups such as branched alkyl groups such as 3-hexyl group; cyclopropyl group, cyclobutyl group, A group in which part or all of the hydrogen atoms of a cycloalkyl group such as a cyclopentyl group, a norbornyl group, and an adamantyl group are substituted with a halogen atom).

As the alkyl group represented by R ³ and R ⁴ , and the cycloalkyl group and aryl group represented by R ³ , for example, the groups exemplified above for R ¹ and R ² can be applied. As the substituent for these groups, for example, the groups exemplified as the substituents for the optionally substituted alkyl group, cycloalkyl group and aryl group represented by R ¹ and R ² can be applied. Examples of the aralkyl group represented by R ³ include an aralkyl group having 7 to 20 carbon atoms. Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group.

Examples of the group having a cyclic ether structure that may be formed by linking R ¹ and R ³ include 2,2-oxetanediyl group, 2,2-tetrahydrofurandiyl group, 2-tetrahydropyrandiyl group, 2 -A dioxane diyl group etc. are mentioned.

In the above R ¹ and R ³ , R ¹ and R ³ are preferably linked to form a cyclic ether structure. Moreover, it is preferable that group represented by the said Formula (1) is group represented by the said Formula (1-1). By making the group represented by the formula (1) into the specific ring structure, the hydrophobicity becomes higher with respect to the developer, and the film thickness reduction can be further suppressed.

  Examples of the structural unit (I) include structural units represented by the following formulas (1-2) to (1-4).

In the above formulas (1-2) to (1-4), R ′ is a hydrogen atom or a methyl group. R ¹ , R ² and R ³ have the same meaning as in the above formula (1).

  Examples of the monomer that gives the structural unit (I) represented by the above formulas (1-2) to (1-4) include 1-ethoxyethyl methacrylate, 1-methoxyethyl methacrylate, 1-n methacrylate. -Butoxyethyl, 1-isobutoxyethyl methacrylate, 1-t-butoxyethyl methacrylate, 1- (2-chloroethoxy) ethyl methacrylate, 1- (2-ethylhexyloxy) ethyl methacrylate, 1-n methacrylate -Propoxyethyl, 1-cyclohexyloxyethyl methacrylate, 1- (2-cyclohexylethoxy) ethyl methacrylate, 1-benzyloxyethyl methacrylate, 2-tetrahydropyranyl methacrylate, 1-ethoxyethyl acrylate, acrylic acid 1 -Methoxyethyl, 1-n-butoxyethyl acrylate, acrylic 1-isobutoxyethyl, 1-t-butoxyethyl acrylate, 1- (2-chloroethoxy) ethyl acrylate, 1- (2-ethylhexyloxy) ethyl acrylate, 1-n-propoxyethyl acrylate, acrylic acid 1-cyclohexyloxyethyl, 1- (2-cyclohexylethoxy) ethyl acrylate, 1-benzyloxyethyl acrylate, 2-tetrahydropyranyl acrylate, 2,3-di (1- (trimethylsilanyloxy) ethoxy) Carbonyl) -5-norbornene, 2,3-di (1- (trimethylgermyloxy) ethoxy) carbonyl) -5-norbornene, 2,3-di (1-methoxyethoxycarbonyl) -5-norbornene, 2,3 -Di (1- (cyclohexyloxy) ethoxycarbonyl) -5-norbol 2,3-di (1- (benzyloxy) ethoxycarbonyl) -5-norbornene, p or m-1-ethoxyethoxystyrene, p or m-1-methoxyethoxystyrene, p or m-1-n- Butoxyethoxystyrene, p or m-1-isobutoxyethoxystyrene, p or m-1- (1,1-dimethylethoxy) ethoxystyrene, p or m-1- (2-chloroethoxy) ethoxystyrene, p or m -1- (2-ethylhexyloxy) ethoxystyrene, p or m-1-n-propoxyethoxystyrene, p or m-1-cyclohexyloxyethoxystyrene, p or m-1- (2-cyclohexylethoxy) ethoxystyrene, p or m-1-benzyloxyethoxystyrene and the like. These monomers can be used alone or in combination of two or more.

  Among these, as the monomer giving the structural unit (I), 1-n-butoxyethyl methacrylate and 2-tetrahydropyranyl methacrylate are preferable.

  As the monomer that gives the structural unit (I), a commercially available monomer may be used, or a monomer synthesized by a known method may be used. For example, the monomer that gives the structural unit (I) represented by the above formula (1-2) is synthesized by reacting (meth) acrylic acid with vinyl ether in the presence of an acid catalyst as shown in the following formula. can do.

In the above formulas, R ', ^{R 1} and ^{R 3} is as defined in the above formula (1-2). R ²¹ and R ²² are the same as R ² in the above formula (1-2) as —CH (R ²¹ ) (R ²² ).

  [A] As a content rate of structural unit (I) in a copolymer, 10 mass%-70 mass% are preferable with respect to all the structural units contained in [A] copolymer, and 20 mass%-60 mass%. % Is more preferable.

[Structural unit (II)]
The structural unit (II) is not particularly limited as long as it has one or more (meth) acryloyloxy groups.

  [A] As a method for introducing the structural unit (II) into the copolymer, for example, a copolymer of a monomer containing an unsaturated compound having at least one hydroxyl group in one molecule (hereinafter referred to as “[A1] copolymer”). And a method of reacting an unsaturated isocyanate compound.

  [A1] Monomers (hereinafter also referred to as “monomer (A1)”) used for the synthesis of the copolymer include (meth) acrylic acid hydroxyalkyl ester, (meth) acrylic acid dihydroxyalkyl ester, ( And (meth) acrylic acid (6-hydroxyhexanoyloxy) alkyl ester.

  Examples of the (meth) acrylic acid hydroxyalkyl ester include (meth) acrylic acid 2-hydroxyethyl ester, (meth) acrylic acid 3-hydroxypropyl ester, (meth) acrylic acid 4-hydroxybutyl ester, and the like. Examples of the (meth) acrylic acid dihydroxyalkyl ester include (meth) acrylic acid 2,3-dihydroxypropyl ester, (meth) acrylic acid 1,3-dihydroxypropyl ester, and (meth) acrylic acid 3,4-dihydroxybutyl ester. Examples include esters. Examples of the (meth) acrylic acid (6-hydroxyhexanoyloxy) alkyl ester include (meth) acrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester and (meth) acrylic acid 3- (6-hydroxyhexa). Noyloxy) propyl ester and the like.

  Among these monomers (A1), from the viewpoint of copolymerization reactivity and reactivity with an isocyanate compound, acrylic acid 2-hydroxyethyl ester, acrylic acid 3-hydroxypropyl ester, acrylic acid 4-hydroxybutyl ester, Methacrylic acid 2-hydroxyethyl ester, methacrylic acid 3-hydroxypropyl ester, methacrylic acid 4-hydroxybutyl ester, acrylic acid 2,3-dihydroxypropyl ester, and methacrylic acid 2,3-dihydroxypropyl ester are preferred. These monomers can be used alone or in combination of two or more.

  The [A1] copolymer obtained as described above may be used for the synthesis of the [A] copolymer in the polymerization reaction solution, and after the [A1] copolymer is once separated from the solution, A] You may use for the synthesis | combination of a copolymer.

  Examples of the unsaturated isocyanate compound include an isocyanate group-containing derivative of (meth) acrylic acid. Examples of the unsaturated isocyanate compound include 2- (meth) acryloyloxyethyl isocyanate, 4- (meth) acryloyloxybutyl isocyanate, 2- (2-isocyanatoethoxy) ethyl (meth) acrylate, 1,1- (bis ( And (meth) acryloyloxymethyl) ethyl isocyanate. In addition, an unsaturated isocyanate compound can be used individually or in mixture of 2 or more types.

  Examples of commercially available unsaturated isocyanate compounds include Karenz AOI (manufactured by Showa Denko) as a commercial product of 2-acryloyloxyethyl isocyanate, Karenz MOI (manufactured by Showa Denko) as a commercial product of 2-methacryloyloxyethyl isocyanate, and methacrylic acid 2 As a commercially available product of-(2-isocyanatoethoxy) ethyl, Karenz MOI-EG (manufactured by Showa Denko), and as a commercially available product of 1,1- (bisacryloyloxymethyl) ethyl isocyanate, Karenz BEI (manufactured by Showa Denko) and the like can be mentioned.

  Among these unsaturated isocyanate compounds, from the viewpoint of reactivity with the [A1] copolymer, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 4-methacryloyloxybutyl isocyanate or methacrylic acid 2- (2 -Isocyanatoethoxy) ethyl, 1,1- (bisacryloyloxymethyl) ethyl isocyanate is preferred.

  [A1] The reaction between the copolymer and the unsaturated isocyanate compound is carried out in the presence of a suitable catalyst, if necessary, in a solution of [A1] copolymer, preferably containing a polymerization inhibitor, at room temperature or under heating. Therefore, it can be carried out by adding the unsaturated isocyanate compound while stirring.

  Examples of the catalyst include di-n-butyltin (IV) dilaurate. Examples of the polymerization inhibitor include p-methoxyphenol.

  [A] As another method for introducing the structural unit (II) into the copolymer, for example, a copolymer of a monomer containing an unsaturated compound having at least one carboxyl group in one molecule (hereinafter referred to as “[ A2] copolymer ”is also reacted with a compound having a vinyl ether group and a (meth) acryloyloxy group.

  [A2] As a method for synthesizing the copolymer, for example, a method of polymerizing a carboxyl group-containing monomer (hereinafter, also referred to as “monomer (A2)”) from the viewpoint of easy acquisition and synthesis of materials. Is mentioned.

  Examples of the monomer (A2) include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic acid monoester, itaconic acid monoester and the like. Of these, (meth) acrylic acid is preferred.

  Examples of the compound having a vinyl ether group and a (meth) acryloyloxy group include a compound represented by the following formula (4).

In the formula (4), ^{R 6} is a hydrogen atom or a methyl group. R ⁷ is a divalent linking group. R ⁸ is a hydrogen atom or a monovalent organic group.

Examples of the divalent linking group represented by R ⁷ include a linear, branched, or cyclic alkylene group having 2 to 18 carbon atoms, an alkoxyalkylene group having 2 to 20 carbon atoms, and 2 to 8 carbon atoms. A halogenated alkylene group, a polyethylene glycol skeleton excluding a terminal hydroxyl group, a polypropylene glycol skeleton excluding a terminal hydroxyl group, a polybutylene glycol skeleton excluding a terminal hydroxyl group, and an aryl group. Examples of the monovalent organic group represented by R ⁸ include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and an optionally substituted aromatic group having 6 to 11 carbon atoms. Is mentioned.

  Examples of the compound having a vinyl ether group and a (meth) acryloyloxy group represented by the above formula (4) include 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, and (meth) acrylic acid. 1-methyl-2-vinyloxyethyl, 2-vinyloxypropyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 1-methyl-3-vinyloxypropyl (meth) acrylate, (meth) acrylic acid 1- Vinyloxymethylpropyl, 2-methyl-3-vinyloxypropyl (meth) acrylate, 1,1-dimethyl-2-vinyloxyethyl (meth) acrylate, 3-vinyloxybutyl (meth) acrylate, (meth) acrylic acid 1 -Methyl-2-vinyloxypropyl, 2-vinyloxybutyl (meth) acrylate, ( T) 4-vinyloxycyclohexyl acrylate, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, 3-vinyloxymethylcyclohexylmethyl (meth) acrylate, (meth) 2-vinyloxymethylcyclohexylmethyl acrylate, p-vinyloxymethylphenylmethyl (meth) acrylate, m-vinyloxymethylphenylmethyl (meth) acrylate, o-vinyloxymethylphenylmethyl (meth) acrylate, ( 2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxy) propyl (meth) acrylate, 2- (meth) acrylic acid 2- ( Vinyloxyethoxy) isopropyl, (meth) acryl 2- (vinyloxyisopropoxy) propyl acid, 2- (vinyloxyisopropoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyl) (meth) acrylate Loxyethoxyisopropoxy) ethyl, 2- (vinyloxyisopropoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxy) (meth) acrylate Ethoxyethoxy) propyl, (meth) acrylic acid 2- (vinyloxyethoxyisopropoxy) propyl, (meth) acrylic acid 2- (vinyloxyisopropoxyethoxy) propyl, (meth) acrylic acid 2- (vinyloxyisopropoxyiso) Propoxy) propyl, (meth) acrylic acid 2- (Vinyloxyethoxyethoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyethoxyisopropoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyisopropoxyethoxy) isopropyl, (meth) acrylic acid 2- (vinyloxy) Isopropoxyisopropoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyethoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (vinyloxyethoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (isopropeno) Xyloxy) ethyl, 2- (isopropenoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropenoxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropenoxyethoxy) (meth) acrylate Ethoxye Kishietokishi) ethyl, (meth) Polyethylene glycol monovinyl ether acrylate, and (meth) acrylic acid polypropylene glycol monovinyl ether. In addition, the compound which has these vinyl ether groups and (meth) acryloyloxy group can be used individually or in mixture of 2 or more types.

  Of these compounds having a vinyl ether group and a (meth) acryloyloxy group, a compound represented by the above formula (4) is preferable, and 2- (vinyloxyethoxy) ethyl (meth) acrylate is more preferable. As commercially available products of 2- (vinyloxyethoxy) ethyl (meth) acrylate, for example, VEEA as 2- (vinyloxyethoxy) ethyl acrylate, VEEM as 2- (vinyloxyethoxy) ethyl methacrylate ( As mentioned above, the product made from Nippon Shokubai etc. is mentioned.

  [A2] The addition reaction between the copolymer and the compound having a vinyl ether group and a (meth) acryloyloxy group is not particularly limited, and can be carried out by adding it to the reaction system. In the above addition reaction, since the [A2] copolymer itself becomes a catalyst, the reaction can be carried out without a catalyst, but a catalyst can also be used in combination.

  [A] As another method for introducing the structural unit (II) into the copolymer, for example, a polyfunctional (meth) acrylate as a monomer is used together with a monomer that gives the structural unit (I) and the like. Examples include a polymerization method.

  Examples of polyfunctional (meth) acrylates include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, triethylene glycol Cyclodecanediyldimethylene di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanate Nurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene Oxide-modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentylglycol di (meth) acrylate, bisphenol A diglycidyl ether both-end (meth) acrylic acid adduct, 1,4-butane Diol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone modified Pentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A di (meth) acrylate, ethylene oxide Examples include modified hydrogenated bisphenol A di (meth) acrylate, propylene oxide modified hydrogenated bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol F di (meth) acrylate, and (meth) acrylate of phenol novolac polyglycidyl ether. These monomers can be used alone or in combination of two or more.

  Examples of commercially available products of polyfunctional (meth) acrylate include SA1002 (Mitsubishi Chemical), Biscoat 195, 230, 260, 215, 310, 214HP, 295, 300, 360, GPT, 400, 700, 540, 3000, 3700 (made by Osaka Organic Chemical Industry), Kayarad R-526, HDDA, NPGDA, TPGDA, MANDA, R-551, R-712, R-604, R -684, PET-30, GPO-303, TMPTA, THE-330, DPHA, DPHA-2H, DPHA-2C, DPHA-2I, D-310, D-330, DPCA-20, DPCA-30, DPCA-60 , DPCA-120, DN-0075, DN-2475, T-1420, T-2020, T-2040 TPA-320, TPA-330, RP-1040, RP-2040, R-011, R-300, R-205 (above, manufactured by Nippon Kayaku), Aronix M-210, M-220, M-233 M-240, M-215, M-305, M-309, M-310, M-315, M-315, M-325, M-400, M-6200, M-6400 (Above, manufactured by Toagosei), light acrylate BP-4EA, BP-4PA, BP-2EA, BP-2PA, DCP-A (above, manufactured by Kyoeisha Chemical), New Frontier BPE-4, BR-42M, GX-8345 (above, manufactured by Daiichi Kogyo Seiyaku), ASF-400 (manufactured by Nippon Steel Chemical), lipoxy SP-1506, SP-1507, SP-1509, SP-4010, SP-4060, V-40 -77, (manufactured by Showa Kobunshi), NK ester A-BPE-4 (Shin-Nakamura Chemical Co., Ltd.).

  Of these polyfunctional (meth) acrylates, compounds having two or more (meth) acryloyloxy groups in the molecule and compounds having three or more (meth) acryloyloxy groups in the molecule are preferred. As a compound having two or more (meth) acryloyloxy groups in the molecule, diethylene glycol di (meth) acrylate is more preferable. Examples of the compound having 3 or more (meth) acryloyloxy groups in the molecule include tri (meth) acrylate compounds, tetra (meth) acrylate compounds, penta (meth) acrylate compounds, hexa (meth) acrylate compounds, and the like. . Among these compounds having three or more (meth) acryloyloxy groups, trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (Meth) acrylate and ditrimethylolpropane tetra (meth) acrylate are preferred.

  [A] The content of the structural unit (II) in the copolymer is preferably 5 mol% or more and 60 mol% or less with respect to all the structural units contained in the [A] copolymer. [A] When the copolymer contains the structural unit (II) at the above-mentioned specific content, the cross-linked structure between the molecular chains is further promoted, and as a result, in addition to better sensitivity and storage stability, the undeveloped relative to the development time. An amount of change in the film thickness of the exposed portion can be further suppressed, and an interlayer insulating film for a display element having more excellent light resistance and heat resistance can be formed.

  The structural unit (II) preferably has two or more (meth) acryloyloxy groups. The structural unit (II) has two or more (meth) acryloyloxy groups, and in addition to better sensitivity and storage stability, the amount of change in the film thickness of the unexposed area with respect to the development time can be further suppressed. The shape stability of the hole can be further improved. In addition, it is possible to form an interlayer insulating film for a display element having excellent light resistance and heat resistance.

[Other structural units]
[A] The copolymer may contain other structural units other than the structural unit (I) and the structural unit (II) as long as the effects of the present invention are not impaired.

  Examples of other structural unit-providing monomers include (meth) acrylic acid, (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid aryl ester, and (meth) acrylic acid aralkyl. Examples include esters, unsaturated dicarboxylic acid dialkyl esters, vinyl aromatic compounds, conjugated diene compounds, and other unsaturated compounds.

Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic sec. -Butyl, (meth) acrylic acid t-butyl etc. are mentioned. Examples of the (meth) acrylic acid cycloalkyl ester include cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and tricyclo [5.2.1.0 ^2,6 ] decane- (meth) acrylate. Examples include 8-yl, 2- (tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxy) ethyl (meth) acrylate, and isobornyl (meth) acrylate. Examples of the (meth) acrylic acid aryl ester include phenyl acrylate. Examples of (meth) acrylic acid aralkyl esters include benzyl (meth) acrylate. Examples of the unsaturated dicarboxylic acid dialkyl ester include diethyl maleate and diethyl fumarate. Examples of the vinyl aromatic compound include styrene and α-methylstyrene. Examples of the conjugated diene compound include 1,3-butadiene and isoprene. Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide. These monomers can be used alone or in combination of two or more.

Among these monomers, from the viewpoint of copolymerization reactivity, (meth) acrylic acid, methyl (meth) acrylate, n-butyl methacrylate, 2-methylglycidyl methacrylate, benzyl methacrylate, tricyclomethacrylate [ 5.2.1.0 ^2,6 ] decan-8-yl, styrene, p-methoxystyrene and 1,3-butadiene are preferred.

[A] The polystyrene-reduced weight average molecular weight (Mw) by gel permeation chromatography (GPC) of the copolymer is preferably 2.0 × 10 ^{3 to} 1.0 × 10 ⁵ , more preferably 5.0 ×. 10 ^{3 to} 5.0 × 10 ⁴ . [A] By making Mw of a copolymer into the said specific range, the sensitivity and alkali developability of the said positive type photosensitive resin composition can be improved.

[A] The number average molecular weight (Mn) in terms of polystyrene by GPC of the copolymer is preferably 2.0 × 10 ^{3 to} 1.0 × 10 ⁵ , more preferably 5.0 × 10 ^{3 to} 5.0 ×. 10 is ^four. [A] By making Mn of a copolymer into the said specific range, the cure reactivity at the time of hardening of the coating film of the said positive type photosensitive resin composition can be improved.

  [A] The molecular weight distribution (Mw / Mn) of the copolymer is preferably 3.0 or less, more preferably 2.6 or less. [A] By setting Mw / Mn of the copolymer to 3.0 or less, the developability of the obtained interlayer insulating film for display elements can be improved.

In addition, Mw and Mn of this specification were measured by GPC under the following conditions.
Apparatus: GPC-101 (made by Showa Denko)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined Mobile phase: Tetrahydrofuran Column temperature: 40 ° C
Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene

  [A] The copolymer can be synthesized by radical copolymerization of monomers giving the above structural units. [A] As the solvent used in the polymerization reaction of the copolymer, for example, the solvents exemplified in the section of [D] solvent, which is a constituent component of the positive photosensitive resin composition described later, can be applied.

  As the polymerization initiator used in the polymerization reaction, those generally known as radical polymerization initiators can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- ( 2,4-Dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile), azo compounds such as 2,2′-azobis (methyl 2-methylpropionate); benzoyl Organic peroxides such as peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) cyclohexane; hydrogen peroxide and the like.

  [A] In the polymerization reaction of the copolymer, a molecular weight modifier may be used to adjust the molecular weight. Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and thioglycolic acid; Xanthogens such as xanthogen sulfide and diisopropylxanthogen disulfide; terpinolene, α-methylstyrene dimer and the like.

<[B] Compound>
The compound [B] is a compound that generates an acid upon irradiation with radiation. As the radiation, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used. When the positive photosensitive resin composition contains the [B] compound, the positive photosensitive resin composition can exhibit positive radiation sensitive characteristics. [B] As the form of inclusion of the compound in the positive-type photosensitive resin composition, the form of the acid generating group incorporated as part of [A] copolymer or other polymer, even in the form of the compound as described below It may be in the form or both forms.

[B] The compound is not particularly limited as long as it is a compound having an oxime sulfonate group represented by the above formula (2). In the above formula (2), R ⁵ is a linear, branched or cyclic alkyl group or aryl group. However, one part or all part of the hydrogen atom which the said alkyl group and aryl group have may be substituted.

The linear, branched or cyclic alkyl group represented by R ⁵ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The linear or branched alkyl group having 1 to 10 carbon atoms may be substituted. Examples of the substituent include an alkoxy group having 1 to 10 carbon atoms and 7,7-dimethyl-2-oxonorbornyl. And an alicyclic group containing a bridged alicyclic group such as a group. A preferred alicyclic group is a bicycloalkyl group. The aryl group represented by R ⁵ is preferably an aryl group having 6 to 11 carbon atoms, and more preferably a phenyl group or a naphthyl group. The aryl group may be substituted, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

  Examples of the compound containing an oxime sulfonate group represented by the above formula (2) include an oxime sulfonate compound represented by the following formula (3).

In the above formula (3), ^{R 5} is as defined in the above formula (2). X is an alkyl group, an alkoxy group, or a halogen atom. m is an integer of 0-3. However, when there are a plurality of Xs, the plurality of Xs may be the same or different.

  The alkyl group that can be represented by X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group represented by X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom represented by X is preferably a chlorine atom or a fluorine atom. As m, 0 or 1 is preferable. In the above formula (3), a compound in which m is 1, X is a methyl group, and the substitution position of X is ortho is preferable.

  Examples of the oxime sulfonate compound represented by the above (3) include compounds represented by the following formulas (3-1) to (3-5).

  The compounds (3-1) to (3-5) are respectively represented by (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino-5H). -Thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-p-toluenesulfonyloxyimino-5H -Thiophen-2-ylidene)-(2-methylphenyl) acetonitrile and (5-octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile, which are commercially available.

  [B] As the compound, a compound represented by the above formula (3) is preferable, and compounds represented by the above formulas (3-1) to (3-5) which are available as commercial products are more preferable.

  The content of the [B] compound in the positive photosensitive resin composition is preferably 0.1 with respect to 100 parts by mass of the [A] copolymer, when the [B] compound is in the form of a compound. It is 10 to 10 parts by mass, more preferably 1 to 5 parts by mass. [B] By adjusting the content of the compound within the above specific range, the sensitivity of the positive photosensitive resin composition is optimized, and while maintaining transparency, an interlayer insulating film for a display element having excellent light resistance and heat resistance is provided. Can be formed.

  In addition, as the compound [B], in addition to the compound having an oxime sulfonate group represented by the above formula (2), an onium salt, a sulfonimide compound, a halogen-containing compound, and a diazomethane compound as long as the effects of the present invention are not impaired. , Sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds and the like may be further contained. In addition, these [B] compounds can be used individually or in combination of 2 or more types.

  Examples of the onium salt include diphenyliodonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, and tetrahydrothiophenium salt. Examples of the diphenyliodonium salt include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyliodonium. Butyltris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoroarsenate Bis (4-t-butylphenyl) iodonium trifluorome Sulphonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium-p-toluenesulfonate, bis (4-t-butylphenyl) iodonium camphorsulfonic acid, etc. . Examples of the triphenylsulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, triphenylsulfonium. And butyl tris (2,6-difluorophenyl) borate. Examples of the sulfonium salt include alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts, substituted benzylsulfonium salts and the like. Examples of the alkylsulfonium salt include 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (Benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate and the like can be mentioned. Examples of the benzylsulfonium salt include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenyl. Methylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenyl Examples include methylsulfonium hexafluorophosphate. Examples of the dibenzylsulfonium salt include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyl dibenzylsulfonium hexafluoroantimonate, and dibenzyl-4-methoxyphenylsulfonium. Hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl- Examples include 4-hydroxyphenylsulfonium hexafluorophosphate. Examples of substituted benzylsulfonium salts include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and p-chlorobenzyl-4-hydroxyphenylmethyl. Sulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3- Examples include chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate. Examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, and 3- (p-methoxybenzyl). ) Benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, and the like. Examples of tetrahydrothiophenium salts include 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate and 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethane. Sulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-1,1 , 2,2-Tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (5-t-butoxycarbonyloxybicyclo) [2.2.1] Heptan-2-yl) -1,1, , 2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (6-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl ) -1,1,2,2-tetrafluoroethanesulfonate and the like.

  Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy). ) Succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N -(2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphenyl monomer Imido, 4-methylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) Diphenylmaleimide, N- (phenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (nonafluorobutane Sulfonyloxy) bicyclo [2.2.1] Pto-5-ene-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-en-2,3-dicarboxylimide, N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5 -Ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenyl) Sulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyl) Ruoxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept- 5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-fluoro Phenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5 , 6-oxy-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-di Ruboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] Heptane-5,6-oxy-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2 , 3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide, N- (camphorsulfonyloxy) naphthyl dicarboxylimide, N- (4-methylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (Phenylsulfonyloxy) naphthyl dicarboxylimide, N- 2-trifluoromethylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (4-fluorophenylsulfonyloxy) naphthyl dicarboxylimide, N- (pentafluoroethylsulfonyloxy) naphthyl dicarboxylimide, N- (heptafluoropropylsulfonyl) Oxy) naphthyl dicarboxylimide, N- (nonafluorobutylsulfonyloxy) naphthyl dicarboxylimide, N- (ethylsulfonyloxy) naphthyl dicarboxylimide, N- (propylsulfonyloxy) naphthyl dicarboxylimide, N- (butylsulfonyl) Oxy) naphthyl dicarboxylimide, N- (pentylsulfonyloxy) naphthyl dicarboxylimide, N- (hexylsulfonyloxy) naphthyl dicarbo Xylimide, N- (heptylsulfonyloxy) naphthyl dicarboxylimide, N- (octylsulfonyloxy) naphthyl dicarboxylimide, N- (nonylsulfonyloxy) naphthyl dicarboxylimide, and the like.

  Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds.

  Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, and bis (2,4-xylylsulfonyl) diazomethane. Bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl (benzoyl) diazomethane Etc.

  Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds, diaryldisulfone compounds, and the like.

  Examples of the sulfonate compound include alkyl sulfonate, haloalkyl sulfonate, aryl sulfonate, and imino sulfonate.

  Examples of the carboxylic acid ester compound include carboxylic acid o-nitrobenzyl ester.

<[C] radical scavenger>
[C] The radical scavenger can decompose radicals generated by exposure or heating in the positive-type photosensitive resin composition or peroxide generated by oxidation, and can prevent the cleavage of the bond of the polymer molecule. It is a possible ingredient. As a result, in the interlayer insulating film for display elements obtained from the positive photosensitive resin composition, the positive photosensitive resin composition can further suppress the change in film thickness.

  Examples of the [C] radical scavenger include compounds having a hindered phenol structure, compounds having a hindered amine structure, compounds having an alkyl phosphite structure, and compounds having a thioether structure.

  Examples of the compound having a hindered phenol structure include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- (3,5-di-). tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tris- (3,5-di-tert-butyl-4-hydroxy Benzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N′-hexane-1,6 -Diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide), 3,3 , 3 ′, 5 ′, 5′-hexa-tert-butyl-a, a ′, a ′-(mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) ) -O-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate, hexamethylene Bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6-xylin) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3 5-to Azine-2-ylamine) phenol, and the like.

  As a commercial item of the compound having the hindered phenol structure, for example, ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80, AO-330 (above, manufactured by ADEKA), Sumizer GM, GS, MDP-S, BBM-S, WX-R, GA-80 (above, manufactured by Sumitomo Chemical), IRGANOX 1010, 1035, 1076 1098, 1135, 1330, 1726, 1425 WL, 1520L, 245, 259, 3114, 565, IRGAMOD295 (above, manufactured by Ciba Japan), Yoshinox BHT, BB, 2246G, 425, 250, 930, SS, TT, 917, 314 (above, API Corporation) Deployment, Ltd.), and the like.

  Examples of the compound having a hindered amine structure include 2,6-di-t-butyl-4-cresol, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, and bis (2,2,6). , 6-Tetramethyl-4-piperidyl) succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (N-octoxy-2,2,6,6-tetramethyl-4) -Piperidyl) sebacate, bis (N-benzyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl) ) Sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-buty Malonate, bis (1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl) 2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate Bis (1,2,2,6,6-pentamethyl-4-piperidyl) decanedioate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4- [3- (3,5-di -T-butyl-4-hydroxyphenyl) propionyloxy] -1- [2- (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy) ethyl] -2,2,6 6-tetramethylpiperidine, 2-methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide , Tet Kiss (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1, 2,3,4-butanetetracarboxylate and the like.

  Examples of commercially available compounds having the hindered amine structure include ADK STAB LA-52, LA57, LA-62, LA-67, LA-63P, LA-68LD, LA-77, and LA-82. LA-87 (manufactured by ADEKA), sumilizer 9A (manufactured by Sumitomo Chemical), CHIMASSORB119FL, 2020FDL, 944FDL, TINUVIN622LD, 144, 765, and 770DF (manufactured by Ciba Japan).

  Examples of the compound having an alkyl phosphite structure include tris (nonylphenyl) phosphite, tris (p-tert-octylphenyl) phosphite, tris [2,4,6-tris (α-phenylethyl)] phosphite. , Tris (p-2-butenylphenyl) phosphite, bis (p-nonylphenyl) cyclohexyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, di (2,4-di-tert) -Butylphenyl) pentaerythritol diphosphite, 2,2'-methylenebis (4,6-di-t-butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus, distearylpentaerythritol diphosphite, 4 , 4'-Isopropylide-diphenol alkyl phosphite Tetratridecyl-4,4′-butylidene-bis (3-methyl-6-tert-butylphenol) diphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenephosphite, 2, 6-di-tert-butyl-4-methylphenylphenylpentaerythritol diphosphite, 2,6-tert-butyl-4-methylphenylphenylpentaerythritol diphosphite, 2,6-di-tert-butyl-4- Ethylphenylstearyl pentaerythritol diphosphite, di (2,6-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,6-di-tert-amyl-4-methylphenylphenylpentaerythritol diphosphite Etc.

  Examples of commercially available compounds having an alkyl phosphite structure include, for example, ADK STAB PEP-4C, PEP-8, PEP-8W, PEP-24G, PEP-36, HP-10, 2112, 260, 522A, 1178, 1500, C, 135A, 3010, TPP (manufactured by ADEKA), IRGAFOS168 (manufactured by Ciba Japan), and the like.

  Examples of the compound having a thioether structure include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis (3-lauryl thiopropionate). , Pentaerythritol tetrakis (3-octadecylthiopropionate), pentaerythritol tetrakis (3-myristylthiopropionate), pentaerythritol tetrakis (3-stearylthiopropionate) and the like.

  Examples of commercially available compounds having a thioether structure include ADK STAB AO-412S, AO-503 (above, manufactured by ADEKA), Sumitizer TPL-R, TPM, TPS, TTP-D, MB (above, Sumitomo Chemical). Product), IRGANOXPS800FD, 802FD (manufactured by Ciba Japan), DLTP, DSTP, DMTP, DTTP (manufactured by API Corporation) and the like.

  Of these [C] radical scavengers, compounds having a hindered phenol structure are preferred, and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3, 5-Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and 2,6-di-t-butyl-4-cresol are more preferable.

  These compounds can be used alone or in combination of two or more. In the positive photosensitive resin composition, the content of the [C] radical scavenger is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 100 parts by mass of the [A] copolymer. Is 0.2 parts by mass or more and 5 parts by mass or less. [C] By making content of a radical scavenger into the said specific range, the said positive type photosensitive resin composition can suppress a film thickness change amount more.

<[D] solvent>
[D] As the solvent, a solvent in which each component is uniformly dissolved or dispersed and does not react with each component is preferably used. [D] Examples of the solvent include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionate. , Aromatic hydrocarbons, ketones, and other esters. In addition, these solvents can be used alone or in combination of two or more.

  Examples of alcohols include methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol and the like.

  Examples of ethers include tetrahydrofuran.

  Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether.

  Examples of the ethylene glycol alkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate.

  Examples of the diethylene glycol alkyl ether include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether.

  Examples of the propylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like.

  Examples of propylene glycol monoalkyl ether acetates include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate and the like.

  Examples of the propylene glycol monoalkyl ether propionate include propylene monoglycol methyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate and the like. .

  Examples of aromatic hydrocarbons include toluene and xylene.

  Examples of ketones include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and the like.

  Examples of other esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, hydroxy Methyl acetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate Methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, Methyl ropoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propylbutoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionate Propyl acid, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butoxypropionic acid Ethyl, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methyl Butyl xylpropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxy Examples include propyl propionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

  Among these solvents, at least one solvent selected from the group consisting of ketones, ethylene glycol monoalkyl ethers, diethylene glycol alkyl ethers, and propylene glycol monoalkyl ether acetates is preferable, diethylene glycol ethyl methyl ether, propylene glycol Monomethyl ether acetate and methyl isobutyl ketone are more preferable. By selecting the specific solvent, it is possible to suppress coating unevenness on the coating surface when a large substrate is applied by a spinless method.

<[E] epoxy compound>
The positive photosensitive resin composition preferably further contains an [E] epoxy compound as a suitable component. When the positive photosensitive resin composition further contains an [E] epoxy compound, the light resistance and heat resistance of the interlayer insulating film for display elements formed from the positive photosensitive resin composition are further improved. be able to.

  [E] The epoxy compound is not particularly limited as long as it is a compound having two or more epoxy groups in the molecule. In addition, the epoxy group referred to in the present specification is a concept including an oxiranyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure).

Examples of the [E] epoxy compound having an oxiranyl group include bisphenol A diglycidyl ether (polycondensate of 4,4′-isopropylidenediphenol and 1-chloro-2,3-epoxypropane), bisphenol F diglycidyl. Ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated Diglycidyl ethers of bisphenol compounds such as bisphenol S diglycidyl ether;
Polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether Glycidyl ether;
Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin;
Phenol novolac type epoxy resin;
Cresol novolac type epoxy resin;
Polyphenol type epoxy resin;
Cycloaliphatic epoxy resin;
Diglycidyl esters of aliphatic long-chain dibasic acids;
Glycidyl esters of higher fatty acids;
Examples include epoxidized soybean oil and epoxidized linseed oil.

  Examples of the [E] epoxy compound having an oxetanyl group include 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis {[1-ethyl (3-oxetanyl)] methyl} ether, bis (3-ethyl-3-oxetanylmethyl) ether and the like.

  Other compounds having two or more 3,4-epoxycyclohexyl groups in the molecule include, for example, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl). -5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4 -Epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-epoxy) of ethylene glycol (Cyclohexylmethyl) A Le, ethylenebis (3,4-epoxycyclohexane carboxylate), lactone-modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane carboxylate and the like.

[E] Commercially available epoxy compounds include, for example, bisphenol A type epoxy resins such as Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 (above, manufactured by Japan Epoxy Resin). Bisphenol F type epoxy resin such as Epicoat 807 (made by Japan Epoxy Resin); phenol novolak such as Epicoat 152, 154, 157S65 (above, made by Japan Epoxy Resin), EPPN201, 202 (above, made by Nippon Kayaku) Type epoxy resin; cresol novolak type epoxy resin such as EOCN102, 103S, 104S, 1020, 1025, 1027 (manufactured by Nippon Kayaku), Epicoat 180S75 (manufactured by Japan Epoxy Resin);
Polyphenol type epoxy resins such as Epicoat 1032H60, XY-4000 (above, Japan Epoxy Resin); CY-175, 177, 179, Araldite CY-182, 192, 184 (above, made by Ciba Specialty Chemicals) ), ERL-4234, 4299, 4221, 4206 (above, manufactured by UCC), Shodyne 509 (made by Showa Denko), Epicron 200, 400 (above, manufactured by Dainippon Ink), Epicoat 871, 872 (Above, made by Japan Epoxy Resin), cyclic aliphatic epoxy resins such as ED-5661, 5862 (above, made by Celanese coating); Epolite 100MF (made by Kyoeisha Chemical), Epiol TMP (made by Nippon Oil & Fats), 1, 4 -Bis [(3-ethyl-3-oxetanylmethoxy) methyl ] Benzene, bis {[1-ethyl (3-oxetanyl)] methyl} and aliphatic polyglycidyl ethers such as ether.

  Among these [E] epoxy compounds, bisphenol A diglycidyl ether (polycondensate of 4,4′-isopropylidenediphenol and 1-chloro-2,3-epoxypropane), bisphenol F diglycidyl ether, phenol novolak Type epoxy resin, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis {[1-ethyl (3-oxetanyl)] methyl} ether, bis (3-ethyl-3-oxetanylmethyl) ) Ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate is preferred.

  [E] Epoxy compounds may be used alone or in combination of two or more. As content of the [E] epoxy compound in the said positive photosensitive resin composition, Preferably it is 0.5 mass part-50 mass parts with respect to 100 mass parts of [A] copolymers, More preferably 1 part by mass to 30 parts by mass. [E] By making content of an epoxy compound into the said specific range, the light resistance and heat resistance of the interlayer insulation film for display elements can be improved more.

<Other optional components>
In addition to the above-mentioned components [A] to [E], the positive photosensitive resin composition includes [F] basic compound, [G] surfactant, quinonediazide as necessary as long as the effects of the present invention are not impaired. You may contain other arbitrary components, such as a compound. These other optional components may be used alone or in combination of two or more. Hereinafter, each component will be described in detail.

<[F] Basic compound>
When the positive photosensitive resin composition contains the [F] basic compound, the diffusion length of the acid generated from the [B] compound by exposure can be appropriately controlled, and the pattern developability can be improved. . [F] The basic compound can be arbitrarily selected from those used in chemically amplified resists, such as aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and carboxylic acid quaternary ammoniums. Examples include salts.

  Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, dicyclohexylamine, Examples include dicyclohexylmethylamine.

  Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.

  Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4 -Dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, pyrazole , Pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4,3,0] -5-nonene, 1,8-diazabicyclo [5,3,0] -7undecene Etc.

  Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.

  Examples of the carboxylic acid quaternary ammonium salt include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

  Of these [F] basic compounds, heterocyclic amines are preferable, and 4-dimethylaminopyridine, 4-methylimidazole, and 1,5-diazabicyclo [4,3,0] -5-nonene are more preferable.

  As content of the [F] basic compound in the said positive photosensitive resin composition, 0.001 mass part-1 mass part are preferable with respect to 100 mass parts of [A] copolymers, 0.005 mass part -0.2 mass part is more preferable. [F] By making content of a basic compound into the said specific range, pattern developability improves more.

<[G] Surfactant>
[G] The surfactant can further improve the film-forming property of the positive photosensitive resin composition. [G] Examples of the surfactant include a fluorine-based surfactant and a silicone-based surfactant. When the positive photosensitive resin composition contains the [G] surfactant, the surface smoothness of the coating film can be improved, and as a result, the thickness uniformity of the interlayer insulating film for display elements formed can be further improved. It can be improved.

  As the fluorosurfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group at at least one of the terminal, main chain and side chain is preferable. For example, 1,1,2,2-tetrafluoro n- Octyl (1,1,2,2-tetrafluoro n-propyl) ether, 1,1,2,2-tetrafluoro n-octyl (n-hexyl) ether, hexaethylene glycol di (1,1,2,2 , 3,3-hexafluoro n-pentyl) ether, octaethylene glycol di (1,1,2,2-tetrafluoro n-butyl) ether, hexapropylene glycol di (1,1,2,2,3,3) -Hexafluoro n-pentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluoro n-butyl) ether, Sodium fluoro n-dodecanesulfonate, 1,1,2,2,3,3-hexafluoro n-decane, 1,1,2,2,3,3,9,9,10,10-decafluoro n- Dodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarboxylate, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkylammonium iodide, fluoroalkylbetaine, fluoroalkylpolyoxyethylene ether, Fluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, carboxylic acid fluoroalkyl ester and the like can be mentioned.

  Examples of commercially available fluorosurfactants include BM-1000, BM-1100 (above, manufactured by BM CHEMIE), MegaFuck F142D, F172, F173, F183, F178, F191, F191, and F471. F476 (above, manufactured by Dainippon Ink and Chemicals), Florard FC-170C, FC-171, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-105, SC-106 (and above) Asahi Glass Co., Ltd.), F-top EF301, EF303, EF352 (above, manufactured by Shin-Akita Kasei), Footent FT-100, FT-110, FT-140A, FT-150, FT-250, FT-251, FT-300, FT-310, FT-400S, FTX-218, FT-251 (above, Neos), etc. Is mentioned.

  Examples of the silicone-based surfactant include Torre Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, and SF-8428. DC-57, DC-190, SH 8400 FLUID (above, manufactured by Toray Dow Corning Silicone), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4252 (above, GE Toshiba Silicone), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

  As content of [G] surfactant in the said positive photosensitive resin composition, Preferably it is 0.01 mass part or more and 2 mass parts or less with respect to 100 mass parts of [A] copolymers, and more. Preferably they are 0.05 mass part or more and 1 mass part or less. [G] The film thickness uniformity of a coating film can be improved more by making content of surfactant into the said specific range.

<Quinonediazide compound>
A quinonediazide compound is a compound that generates a carboxylic acid upon irradiation with radiation. As the quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide can be used.

  Examples of the mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother nuclei.

  Examples of trihydroxybenzophenone include 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone. Examples of tetrahydroxybenzophenone include 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3 , 4,2′-tetrahydroxy-4′-methylbenzophenone, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone, and the like. Examples of pentahydroxybenzophenone include 2,3,4,2 ', 6'-pentahydroxybenzophenone. Examples of hexahydroxybenzophenone include 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone and 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone. Examples of (polyhydroxyphenyl) alkanes include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tris (p-hydroxy). Phenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl-) 4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl) -4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiy Den -5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl -7,2 ', 4'-trihydroxy flavan like. Examples of other mother nucleus include 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 1- [1- (3- {1- (4- Hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4, 6-dihydroxyphenyl) -1-methylethyl) benzene and 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene.

  Among these mother nuclei, 2,3,4,4′-tetrahydroxybenzophenone, 1,1,1-tri (p-hydroxyphenyl) ethane, 4,4 ′-[1- [4- [1- [ 4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol is preferred.

  As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable. Examples of 1,2-naphthoquinonediazide sulfonic acid chloride include 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, and the like. Of these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is preferred.

  As a condensate of a phenolic compound or an alcoholic compound and 1,2-naphthoquinone diazide sulfonic acid halide, 1,1,1-tri (p-hydroxyphenyl) ethane and 1,2-naphthoquinone diazide-5-sulfonic acid Condensate with chloride, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide-5-sulfonic acid chloride A condensate with is preferred.

  In the condensation reaction of a phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazide sulfonic acid halide, preferably 30 mol% to 85 mol based on the number of OH groups in the phenolic compound or alcoholic compound. 1,2-naphthoquinonediazide sulfonic acid halide corresponding to mol%, more preferably 50 mol% to 70 mol% can be used. The condensation reaction can be carried out by a known method.

  Examples of the quinonediazide compound include 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, such as 2,3,4-triaminobenzophenone-1,2-naphthoquinonediazide- 4-sulfonic acid amide and the like are also preferably used.

<Preparation method of positive photosensitive resin composition>
The positive photosensitive resin composition is obtained by mixing the [D] solvent with the [A] copolymer, the [B] compound, the [C] radical scavenger, and a suitable component and other optional components as necessary. Prepared in a dissolved or dispersed state. For example, the positive photosensitive resin composition can be prepared by mixing each component at a predetermined ratio in the solvent [D].

<Method for forming interlayer insulating film for display element>
The positive photosensitive resin composition is suitable as a material for forming an interlayer insulating film for display elements. Further, the present invention suitably includes an interlayer insulating film for a display element formed from the positive photosensitive resin composition.

The method for forming an interlayer insulating film for a display element according to the present invention includes:
(1) The process of forming the coating film of the said positive type photosensitive resin composition on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) a step of developing the coating film irradiated with the radiation; and (4) a step of heating the developed coating film.

  According to this forming method, in addition to excellent light resistance and heat resistance, it is possible to form an interlayer insulating film for a display element with a small amount of change in film thickness of an unexposed portion with respect to development time. Furthermore, the stability of the contact hole diameter can be improved. Further, since the amount of film thickness reduction can be suppressed, the production process margin can be improved as a result, and the yield can be improved. Furthermore, an interlayer insulating film for a display element having a fine and elaborate pattern can be easily formed by forming a pattern by exposure, development and heating utilizing photosensitivity. Therefore, the formed interlayer insulation film for display elements can be used suitably for display elements, such as a liquid crystal display element and an organic EL display element.

[Step (1)]
In this step, the positive photosensitive resin composition is applied onto a substrate to form a coating film. Preferably, the solvent is removed by prebaking the coated surface.

  Examples of the substrate include glass, quartz, silicone, and resin. Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, a ring-opening polymer of cyclic olefin, and a hydrogenated product thereof. As prebaking conditions, although it changes also with kinds, compounding ratios, etc. of each component, it can be set as 70 degreeC-120 degreeC, about 1 minute-10 minutes.

[Step (2)]
In this step, at least a part of the formed coating film is exposed to radiation and exposed. When exposing, it exposes normally through the photomask which has a predetermined pattern. As the radiation used for exposure, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation containing ultraviolet light of 365 nm is more preferable. Energy of exposure intensity at the wavelength 365nm radiation, by the value measured by luminometer (OAI model356, OAI Optical Ltd. ^Associates), is preferably ^{500J / m 2 ~6,000J / m 2} , 1,500J / m 2 ˜1,800 J / m ² is more preferable.

[Step (3)]
In this step, the coating film irradiated with the radiation is developed. By developing the coated film after exposure, unnecessary portions (radiation irradiated portions) are removed to form a predetermined pattern. As the developer used in the development step, an alkaline aqueous solution is preferable. Examples of the alkali include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. .

  An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, or a surfactant can be added to the alkaline aqueous solution. The concentration of alkali in the aqueous alkali solution is preferably from 0.1% by mass to 5% by mass from the viewpoint of obtaining appropriate developability. Examples of the developing method include a liquid piling method, a dipping method, a rocking dipping method, and a shower method. The development time varies depending on the composition of the positive photosensitive resin composition, but is about 10 seconds to 180 seconds. Subsequent to such development processing, for example, washing with running water is performed for 30 seconds to 90 seconds, and then a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen.

[Step (4)]
In this step, the developed coating film is heated. For heating, the patterned thin film is heated by using a heating device such as a hot plate or an oven, thereby promoting the curing reaction of the [A] copolymer and obtaining a cured product. As heating temperature, it is about 120 to 250 degreeC, for example. The heating time varies depending on the type of heating device, but for example, it is about 5 to 30 minutes for a hot plate and about 30 to 90 minutes for an oven. Moreover, the step baking method etc. which perform a heating process 2 times or more can also be used. In this way, a patterned thin film corresponding to the target display element interlayer insulating film can be formed on the surface of the substrate. Note that the use of the cured film is not limited to the interlayer insulating film for display elements, and can also be used as a spacer or a protective film.

  The film thickness of the formed interlayer insulating film for display element is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm.

  EXAMPLES Hereinafter, although this invention is explained in full detail based on an Example, this invention is not interpreted limitedly based on description of this Example.

<Synthesis of [A] Component>
[Synthesis Example 1]
A flask equipped with a condenser and a stirrer was charged with 5 parts by mass of 2,2′-azobisisobutyronitrile and 250 parts by mass of propylene glycol monomethyl ether acetate as a polymerization initiator, and subsequently the structural unit (I) was added. 55 parts by weight of 1-n-butoxyethyl methacrylate, 30 parts by weight of 2-hydroxyethyl methacrylate as monomer (A1), and 10 parts by weight of methacrylic acid and 5 parts by weight of styrene to give other structural units After charging and purging with nitrogen, the temperature of the solution was raised to 70 ° C. while gently stirring, and this temperature was maintained for 5 hours to perform polymerization, thereby solidifying the [A1] copolymer solution having a solid content concentration of 28.8% Got. Mw of the obtained [A1] copolymer was 13,000.
[A1] 12 parts by mass of 2-methacryloyloxyethyl isocyanate (Karenz MOI, Showa Denko) as an unsaturated isocyanate compound and 0.1 part by mass of 4-methoxyphenol as a polymerization inhibitor are added to the copolymer solution. After that, the mixture was reacted by stirring at 40 ° C. for 1 hour and further at 60 ° C. for 2 hours. The progress of the reaction between the isocyanate group derived from 2-methacryloyloxyethyl isocyanate and the hydroxyl group of the [A1] copolymer was confirmed by IR (infrared absorption) spectrum. The IR spectrum of the reaction solution after 1 hour at 40 ° C. and further 2 hours at 60 ° C. was measured, and the peak near 2,270 cm ⁻¹ derived from the isocyanate group of 2-methacryloyloxyethyl isocyanate decreased. It was confirmed that the reaction was progressing. A copolymer (A-1) solution having a solid content concentration of 31.0% was obtained. Mw of the copolymer (A-1) was 14,000. As a result of ¹³ C-NMR analysis, the content of each structural unit was structural unit (I): structural unit (II): other structural unit = 42: 31: 27 (mol%). In addition, the ¹³ C-NMR analysis for calculating | requiring the content rate of each structural unit of a polymer used the nuclear magnetic resonance apparatus (the JEOL make, JNM-ECX400).

[Synthesis Example 2]
Synthesis Example 1 except that 19 parts by mass of 1,1- (bisacryloyloxymethyl) ethyl isocyanate (Karenz BEI, Showa Denko) as an unsaturated isocyanate compound was added in place of the 2-methacryloyloxyethyl isocyanate. The copolymer (A-2) solution was obtained by operating in the same manner as above. Mw of the copolymer (A-2) was 15,000. The solid content concentration was 32.0% by mass. As a result of ¹³ C-NMR analysis, the content of each structural unit was structural unit (I): structural unit (II): other structural unit = 42: 30: 28 (mol%).

[Synthesis Example 3]
Into a four-necked flask equipped with a thermometer, a stirrer, and a condenser, was charged 540 parts by mass of diethylene glycol ethyl methyl ether. As a polymerization initiator, 87 parts by mass of 2-tetrahydropyranyl methacrylate that gives structural unit (I), 90 parts by mass of methacrylic acid as monomer (A2), 40 parts by mass of methyl methacrylate that gives other structural units, and 10 parts by mass of 2,2′-azobisisobutyronitrile was added and maintained at the same temperature for 6 hours. Then, after heating up to 100 degreeC and maintaining temperature for 2 hours, [A2] copolymer solution was obtained. To this copolymer solution, 0.2 parts by mass of 4-methoxyphenol as a polymerization inhibitor was added, and then 2- (vinyloxyethoxy) ethyl methacrylate as a compound having a vinyl ether group and a (meth) acryloyloxy group ( 128 parts by mass of VEEM (manufactured by Nippon Shokubai Co., Ltd.) was dropped at a constant rate with a dropping funnel over 1 hour. After the aging reaction for 12 hours, the reaction solution was cooled to room temperature to obtain a copolymer (A-3) solution. Mw of the copolymer (A-3) was 18,000. The solid content concentration was 37.5% by mass. As a result of ¹³ C-NMR analysis, the content of each structural unit was structural unit (I): structural unit (II): other structural units = 26: 50: 24 (mol%).

[Synthesis Example 4]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 57 parts by mass of 2-tetrahydropyranyl methacrylate giving structural unit (I), 8 parts by mass of ethylene glycol dimethacrylate as polyfunctional (meth) acrylate, 10 parts by mass of methacrylic acid giving other structural units, and methacrylic acid After 20 parts by mass of methyl and 3 parts by mass of α-methylstyrene dimer as a molecular weight modifier were charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a copolymer solution containing the copolymer (A-4). Mw of the copolymer (A-4) was 15,000. The solid content concentration was 31.5% by mass. As a result of ¹³ C-NMR analysis, the content of each structural unit was structural unit (I): structural unit (II): other structural unit = 48: 6: 46 (mol%).

[Synthesis Example 5]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 30 parts by mass of 2-tetrahydropyranyl methacrylate, which gives structural unit (I), 20 parts by mass of ethylene glycol dimethacrylate as polyfunctional (meth) acrylate and 50 parts by mass of trimethylolpropane trimethacrylate, and a molecular weight regulator After 3 parts by mass of α-methylstyrene dimer was charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a copolymer solution containing the copolymer (A-5). Mw of the copolymer (A-5) was 20,000. The solid content concentration was 33.5% by mass. As a result of ¹³ C-NMR analysis, the content of each structural unit was structural unit (I): structural unit (II) = 40: 60 (mol%).

[Synthesis Example 6]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator and 400 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 57 parts by mass of 2-tetrahydropyranyl methacrylate giving structural unit (I), 8 parts by mass of ethylene glycol dimethacrylate as polyfunctional (meth) acrylate, 10 parts by mass of methacrylic acid giving other structural units, and methacrylic acid After 20 parts by mass of methyl and 3 parts by mass of α-methylstyrene dimer as a molecular weight modifier were charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-6). Further, 50 parts by mass of trimethylolpropane trimethacrylate as a polyfunctional (meth) acrylate was dropped into the copolymer solution over 1 hour with a dropping funnel, and then stirred for 1 hour. Mw of the copolymer (A-6) was 25,000. The solid content concentration was 26.5% by mass. As a result of ¹³ C-NMR analysis, the content of each structural unit was structural unit (I): structural unit (II): other structural unit = 48: 6: 46 (mol%).

[Synthesis Example 7]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 40 parts by mass of 1-ethoxyethyl methacrylate giving structural unit (I), 5 parts by mass of methacrylic acid, 5 parts by mass of styrene, 10 parts by mass of 2-hydroxyethyl methacrylate and 40 parts by mass of glycidyl methacrylate giving other structural units. Was added, and the mixture was purged with nitrogen. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a copolymer solution containing a copolymer (CS-1). The Mw of the copolymer (CS-1) was 10,000. The solid content concentration was 32.1% by mass.

<Synthesis of [E] epoxy compound>
[Synthesis Example 8]
A flask equipped with a condenser and a stirrer was charged with 8 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 15 parts by weight of methacrylic acid, 20 parts by weight of methyl methacrylate, 30 parts by weight of benzyl methacrylate, 5 parts by weight of styrene, and 30 parts by weight of glycidyl methacrylate were charged with nitrogen, and then the temperature of the solution was gradually stirred. Was raised to 70 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a solution containing the copolymer (E-4). Mw of the copolymer (E-4) was 8,000. Solid content concentration was 32.3 mass%.

<Preparation of positive photosensitive resin composition>
Hereinafter, the components used for the preparation of the positive photosensitive resin compositions of Examples and Comparative Examples will be described in detail.

[B] Component B-1: (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (manufactured by Ciba Specialty Chemicals, IRGACURE PAG 103)
B-2: (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (manufactured by Ciba Specialty Chemicals, IRGACURE PAG 108)
B-3: (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (Ciba Specialty Chemicals, IRGACURE PAG 121)
B-4: (Camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (CGI 1380, manufactured by Ciba Specialty Chemicals)
B-5: (5-octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile (manufactured by Ciba Specialty Chemicals, CGI725)
b-1 (quinonediazide compound): 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2- Condensate with naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol)

[C] radical scavenger C-1: 2,6-di-t-butyl-4-cresol C-2: 1,3,5-trimethyl-2,4,6-tris (3,5-di-t -Butyl-4-hydroxybenzyl) benzene (manufactured by ADEKA, ADEKA STAB AO-330)
C-3: Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate (manufactured by ADEKA, ADEKA STAB LA-57)
C-4: Distearyl pentaerythritol diphosphite (manufactured by ADEKA, ADEKA STAB PEP-8)
C-5: Pentaerythritol tetrakis (3-laurylthiopropionate) (manufactured by ADEKA, ADEKA STAB AO-412S)

[D] Solvent D-1: Methyl isobutyl ketone D-2: Diethylene glycol ethyl methyl ether D-3: Propylene glycol monomethyl ether acetate

[E] Epoxy compound E-1: Phenol novolac type epoxy resin E-2: Bisphenol A diglycidyl ether (polycondensate of 4,4′-isopropylidenediphenol and 1-chloro-2,3-epoxypropane)
E-3: Bis (3-ethyl-3-oxetanylmethyl) ether E-5: 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate

[F] Basic compound F-1: 4-dimethylaminopyridine F-2: 4-methylimidazole

[G] Surfactant G-1: Silicone surfactant (manufactured by Toray Dow Corning Silicone, SH 8400 FLUID)
G-2: Fluorosurfactant (manufactured by Neos, Factent FTX-218)

[Example 1]
[D] A solution containing (A-1) as a copolymer (A-1) in (D-1) as a solvent (amount corresponding to 100 parts by mass (solid content) of (A-1)) B] 3.0 parts by mass of (B-1) as a compound, 0.5 parts by mass of (C-1) as a [C] radical scavenger, (E-1) 5.0 as an [E] epoxy compound A positive photosensitive resin composition was prepared by mixing 0.20 parts by mass of (G-1) as a [G] surfactant and filtering with a membrane filter having a pore size of 0.2 μm.

[Examples 2 to 10 and Comparative Examples 1 and 2]
Each positive photosensitive resin composition was prepared in the same manner as in Example 1 except that the types and blending amounts of each component were as described in Table 1. In Table 1, “-” indicates that the corresponding component was not used. Moreover, the value of the [D] solvent used in Table 1 is a mass ratio when a mixed solvent is used.

<Evaluation>
The following evaluation was implemented using each prepared positive photosensitive resin composition. The results are shown in Table 1.

[Sensitivity (J / m ² )]
Hexamethyldisilazane (HMDS) was applied on a 550 × 650 mm chromium-deposited glass and heated at 60 ° C. for 1 minute. Each positive photosensitive resin composition is applied onto the chromium-deposited glass after HMDS treatment using a slit die coater (manufactured by Tokyo Ohka Kogyo Co., Ltd., TR6322105-CL), and the ultimate pressure is set to 100 Pa under vacuum. After removing the solvent at, the film was further pre-baked at 90 ° C. for 2 minutes to form a coating film having a thickness of 4.0 μm. Subsequently, using an exposure machine (manufactured by Canon, MPA-600FA, ghi line mixture), the coating film was irradiated with radiation with a proxy gap of 10 μm and an exposure amount as a variable through a mask having a contact hole pattern of 10 μm. . Then, it developed for 70 second at 25 degreeC with 0.5 mass% tetramethylammonium hydroxide aqueous solution. Next, washing with running ultrapure water was performed, followed by drying to form a pattern on the glass substrate after the HMDS treatment. At this time, the exposure amount closest to the contact hole diameter of 10 μm was defined as radiation sensitivity. When this value was 500 (J / m ² ) or less, it was judged that the sensitivity was good.

[Appearance of coating film]
Each of the prepared positive photosensitive resin compositions was applied onto a 550 × 650 mm chromium-deposited glass using a slit die coater (manufactured by Tokyo Ohka Kogyo Co., Ltd., TR6322105-CL) and dried under reduced pressure to 0.5 Torr. Pre-baked on a plate at 100 ° C. for 2 minutes to form a coating film, and further exposed at an exposure amount of 2,000 J / m ² to form a film with a thickness of 4 μm from the top surface of the chromium film-forming glass. did. Under the sodium lamp, the appearance of the coating film was observed with the naked eye. At this time, streak unevenness (one or a plurality of straight line unevenness that can be applied or crossed in the direction of application), haze unevenness (cloudy unevenness), pin mark unevenness (points that can be formed on the substrate support pins) The appearance situation of the unevenness of the shape was investigated. "A" (determined as good) when almost none of these unevenness is visible, "B" (determined as slightly bad) when any of them is slightly visible, "C" (determined as bad) when clearly visible It was.

[Thickness change rate (%)]
HMDS was applied on an alkali-free glass substrate and heated for 3 minutes. Each positive photosensitive resin composition was applied using a spinner and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 4.1 μm. The obtained coating film was exposed through a contact hole pattern mask with an exposure gap of 30 μm and operated in the same manner as in the sensitivity evaluation. Subsequently, development was performed by a paddle method at 23 ° C. with a 0.5 mass% tetramethylammonium hydroxide aqueous solution. At this time, the development time was changed to 50 seconds, 70 seconds, and 90 seconds. Thereafter, rinsing was performed with ultrapure water for 8 seconds. It measured about the film thickness of the unexposed part after image development, and calculated the film thickness change rate (%) from this value and the following formula.
Film thickness change rate after development (%) = (film thickness after development / film thickness before development) × 100
Even when the development time was changed to 50 seconds, 70 seconds, and 90 seconds, when the film thickness change rate was 90% or more, the amount of film thickness decrease with respect to the development time could be suppressed, and it was judged good.

[Contact hole shape stability (μm)]
The coating film was formed on the alkali-free glass substrate by operating in the same manner as the evaluation of the film thickness change rate, and the plate temperature was changed to 80 ° C., 90 ° C. and 100 ° C. Thereafter, the same operation as in the evaluation of the film thickness change rate was performed except that the development time was 90 seconds. After exposure through a contact hole mask having a mask size of 10 μm, development was performed to form a contact hole pattern. Thereafter, post-baking was performed in a clean oven at 220 ° C. for 45 minutes. The contact hole pattern formed under each pre-bake temperature condition was observed with an SEM (scanning electron microscope), and the shape and the size of the contact hole pattern were measured. When the size of the contact hole pattern was 9.0 μm to 11.0 μm, it was judged that the shape stability (μm) of the contact hole with respect to the change in the prebake temperature was good.

[Light resistance (%)]
Each positive type photosensitive resin composition is coated on a non-alkali glass substrate in the same manner as in the evaluation of the change rate of the film thickness, prebaked at 90 ° C. for 2 minutes, and a coating film having a film thickness of 3.0 μm is formed. Formed. Thereafter, without exposure, the film was developed with an aqueous solution of 0.5% by mass of tetramethylammonium hydroxide at 25 ° C. for 70 seconds. Thereafter, post-baking was performed in a clean oven at 220 ° C. for 45 minutes. The light transmittance at 400 nm of the obtained cured film was measured (T1). Thereafter, the cured film was irradiated with an Xe lamp (illuminance: 180 W / m ² ) for 70 hours. The light transmittance at 400 nm of the cured film after irradiation was measured (T2). From these values and the following formula, the change rate (%) of the light transmittance before and after irradiation was calculated by the following formula, and this was defined as the light resistance (%).
Light resistance (%) = {(T1-T2) / T1} × 100
When the value was 5% or less, it was judged that the light resistance was good.

[Heat-resistant(%)]
TGA (thermogravimetric analysis) of the post-baked cured film obtained by the above light resistance evaluation was performed using Q5000SA manufactured by TA Instruments. The temperature was raised from room temperature to 250 ° C. in 20 minutes, and then held at 250 ° C. for 10 minutes to measure weight loss. The weight at room temperature before the measurement was taken as 100%, and the weight reduction rate (%) after the measurement was measured to determine the heat resistance (%). When the value was 5% or less, it was judged that heat loss was small and heat resistance was good.

[Storage stability (%)]
By operating in the same manner as the rate of change in film thickness, a coating film of each positive photosensitive resin composition immediately after preparation was formed and the film thickness was measured (in the following formula, referred to as “film thickness immediately after preparation”). In addition, each positive photosensitive resin composition was stored at 30 ° C. for 14 days, and the film thickness of the coating film formed in the same manner after 14 days was measured (in the following formula, referred to as “film thickness after 14 days”). The rate of increase in film thickness (%) was calculated from the following formula and was defined as storage stability (%).
Storage stability (%) = {(film thickness after 14 days−film thickness immediately after preparation) / film thickness immediately after preparation} × 100
When the value was 5% or less, it was judged that the storage stability was good.

  As is apparent from the results of Table 1, Examples 1 to 10 using the positive photosensitive resin composition have better sensitivity and storage stability than the compositions of Comparative Examples 1 and 2, and It was found that the amount of change in the film thickness of the unexposed area with respect to the development time was small. Further, it was found that the interlayer insulating film for display element formed from the positive photosensitive resin composition is excellent in contact hole shape stability in addition to light resistance and heat resistance.

  The positive photosensitive resin composition of the present invention can suppress the change in film thickness of the unexposed part with respect to the development time in addition to good sensitivity and storage stability, and has excellent light resistance and heat resistance. An insulating film can be provided. In addition, the stability of the contact hole diameter can be improved. Since the film thickness reduction amount can be suppressed, the production process margin can be improved as a result, and the yield can be improved. Furthermore, an interlayer insulating film for a display element having a fine and elaborate pattern can be easily formed by forming a pattern by exposure, development and heating utilizing photosensitivity. Therefore, the formed interlayer insulation film for display elements can be used suitably for display elements, such as a liquid crystal display element and an organic EL display element.

Claims (10)

[A] a copolymer comprising a structural unit (I) having a group represented by the following formula (1) and a structural unit (II) having one or more (meth) acryloyloxy groups;
[B] a compound having an oxime sulfonate group represented by the following formula (2):
[C] a radical scavenger, and [D] a solvent,
The structural unit (II) is
(A) structural units and (meth) having a hydroxyl group reactant with the isocyanate group-containing derivatives of acrylic acid,
(B) a structural unit and a vinyl ether group having a carboxy group and (meth) acryloyl reactant with a compound having a oxy group, and (c) structural units derived from the polyfunctional (meth) acrylate as a monomer
A positive photosensitive resin composition that is at least one of the above.

(In formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, provided that the hydrogen atom of the alkyl group, cycloalkyl group and aryl group is A part or all of them may be substituted, and R ¹ and R ² are not both hydrogen atoms, and R ³ is an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, or —M ( R ⁴ ) is a group represented by _3. M is Si, Ge or Sn, each R ⁴ is independently an alkyl group, and R ¹ and R ³ are linked to form a cyclic group. An ether structure may be formed, provided that a part or all of the hydrogen atoms of these groups represented by R ³ may be substituted.)

(In formula (2), R ⁵ is a linear, branched or cyclic alkyl group or aryl group, provided that part or all of the hydrogen atoms of the alkyl group and aryl group are substituted. May be.) The positive photosensitive resin composition according to claim 1, wherein R ¹ and R ³ are linked to form a cyclic ether structure. The positive photosensitive resin composition according to claim 2, wherein the group represented by the formula (1) is a group represented by the following formula (1-1).

  [A] The positive photosensitive resin composition according to claim 1, wherein the content of the structural unit (II) in the copolymer is 5 mol% or more and 60 mol% or less.   The positive photosensitive resin composition according to any one of claims 1 to 4, wherein the structural unit (II) has two or more (meth) acryloyloxy groups.   [D] The solvent according to claim 1, wherein the solvent is at least one solvent selected from the group consisting of ketones, ethylene glycol monoalkyl ethers, diethylene glycol alkyl ethers and propylene glycol monoalkyl ether acetates. The positive photosensitive resin composition according to any one of the above.   [E] The positive photosensitive resin composition according to any one of claims 1 to 6, further comprising a compound having two or more epoxy groups in the molecule.   The positive photosensitive resin composition of any one of Claims 1-7 used for formation of the interlayer insulation film for display elements. (1) The process of forming the coating film of the positive photosensitive resin composition of Claim 8 on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) A method of forming an interlayer insulating film for a display element, comprising: a step of developing the coating film irradiated with the radiation; and (4) a step of heating the developed coating film.   The interlayer insulation film for display elements formed from the positive photosensitive resin composition of Claim 8.