KR101336148B1 - Positive photosensitive composition, interlayer insulating film for diaplay device and its forming method - Google Patents

Abstract

(Problem) The present invention provides, in addition to good sensitivity and storage stability, a positive photosensitive resin composition having a small amount of change in film thickness of an unexposed portion with respect to development time, an interlayer insulating film for display elements having excellent light resistance and heat resistance, and a method of forming the same. It aims to do it.
(Solution means) This invention is a copolymer containing the structural unit (I) which has group represented by [A] following formula (1), and the structural unit (II) which has one or more (meth) acryloyloxy groups, [ B] Positive type photosensitive resin composition containing the compound which has an oxime sulfonate group represented by following formula (2), a [C] radical scavenger, and a [D] solvent.

Description

Positive photosensitive resin composition, interlayer insulating film for display element and method of forming the same {POSITIVE PHOTOSENSITIVE COMPOSITION, INTERLAYER INSULATING FILM FOR DIAPLAY DEVICE AND ITS FORMING METHOD}

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

In the display element, an interlayer insulating film for display elements is formed for the purpose of insulating between wirings arranged in a layer shape. As a formation material of the interlayer insulation film for display elements, positive type photosensitive resin composition is used widely because the number of processes for obtaining a required pattern shape is small, and high flatness is calculated | required by the obtained interlayer insulation film for display elements obtained. Such a positive photosensitive resin composition requires good sensitivity and storage stability, and in addition to the above flatness, excellent light resistance, heat resistance and the like are required for the interlayer insulating film for display elements.

As such a positive photosensitive resin composition, acrylic resin is widely employ | adopted, for example, the composition containing a crosslinking agent, an acid generator, and alkali-soluble resin is known (refer Japanese Unexamined-Japanese-Patent No. 2004-4669). The said alkali-soluble resin means the resin which has a protecting group (group which is insoluble or poorly soluble in alkaline aqueous solution, and can be dissociated by the action of an acid), and becomes soluble in aqueous alkali solution which is a developing solution after this protecting group is dissociated by exposure. . Moreover, as other positive photosensitive resin composition, the positive photosensitive resin composition containing the acetal structure and / or a ketal structure, resin containing an epoxy group, and an acid generator is proposed (refer Japanese Unexamined-Japanese-Patent No. 2004-264623). .

However, when attempting to form the interlayer insulation film for display elements using a conventional positive photosensitive resin composition, the film thickness reduction amount of the unexposed portion in the developing step is large, and the flatness of the interlayer insulation film for display elements is damaged, or the design film is There is a problem that a deviation from the thickness occurs. In addition, in order to avoid this problem, it is necessary to strictly adjust the developing time, which leads to inefficiency of the production process.

In view of such a situation, in addition to the positive type photosensitive resin composition which has favorable sensitivity and storage stability, and excellent light resistance and heat resistance, development of the interlayer insulation film for display elements with a small amount of film thickness change with respect to developing time is desired. .

Japanese Laid-Open Patent Publication No. 2004-4669 Japanese Patent Application Laid-Open No. 2004-264623

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

According to an aspect of the present invention,

[A] A copolymer comprising a structural unit (I) having a group represented by the following formula (1) and a structural unit (II) having at least one (meth) acryloyloxy group (hereinafter, "[A] copolymer" Also called),

[B] A compound having an oxime sulfonate group represented by the following Formula (2) (hereinafter also referred to as "[B] compound"),

[C] radical scavengers, and

[D] is a positive photosensitive resin composition containing a solvent:

(In formula (1), R <^1> and R <^2> is a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group each independently; However, even if one part or all part of the hydrogen atom which the said alkyl group, the cycloalkyl group, and the aryl group have is substituted, And R ¹ and R ² are not all 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 ; R ⁴ is each independently an alkyl group, and R ¹ and R ³ may be linked to each other to form a cyclic ether structure, provided that some or all of the hydrogen atoms of these groups represented by R ³ are May be substituted);

(In formula (2), R <^5> is a linear, branched, or cyclic alkyl group or an 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 group represented by the formula (1) possessed by the structural unit (I) exists as a group (acid dissociable group) which is dissociated in the presence of an acid to generate a polar group, and thus is generated from the compound [B] by irradiation with radiation. It is dissociated by an acid and as a result, the [A] copolymer which was alkali insoluble becomes alkali-soluble. In addition, since the [A] copolymer contains the structural unit (II) having the specific structure, a crosslinked structure is formed between the molecular chains, and in addition to good sensitivity and storage stability, the film thickness variation of the unexposed portion with respect to the development time Not only can be suppressed, but also the formation of the interlayer insulating film for display elements having excellent light resistance and heat resistance is made possible. In addition, the [C] radical scavenger contained in the positive photosensitive resin composition can decompose radicals generated by exposure or heating, or peroxides generated by oxidation, thereby decomposing dissociation of bonds of polymer molecules. It is an ingredient that can be prevented. As a result, the said positive photosensitive resin composition can suppress the film thickness change amount more.

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

By making the group represented by said Formula (1) into the said specific ring structure, hydrophobicity becomes high with respect to a developing solution, and the amount of film thickness reduction can be suppressed more.

It is preferable that the content rate of structural unit (II) in the copolymer (A) is 5 mol% or more and 60 mol% or less. When the copolymer (A) contains the structural unit (II) at the above specific content rate, the crosslinked structure between the molecular chains is further promoted, and as a result, the film thickness variation of the unexposed portion with respect to the development time is further enhanced. Not only can be further suppressed, but also the formation of an interlayer insulating film for a display element having better light resistance and heat resistance is made possible.

It is preferable that structural unit (II) has two or more (meth) acryloyloxy groups. When structural unit (II) has two or more (meth) acryloyloxy groups, in addition to the more favorable sensitivity and storage stability, the film thickness change of the unexposed part with respect to developing time can be further suppressed, and the shape of a contact hole Stability 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 said specific solvent, application | coating nonuniformity of a coating film surface can be suppressed, for example, when apply | coating a large sized board | substrate by a spinless method.

It is preferable that the positive photosensitive resin composition further contains a compound having two or more epoxy groups (hereinafter also referred to as "[E] epoxy compound") in the [E] molecule. When the positive photosensitive resin composition further contains the [E] epoxy compound, the light resistance and the heat resistance of the interlayer insulating film for display element formed of the positive photosensitive resin composition can be further improved.

The said positive photosensitive resin composition is suitable as a formation material of the interlayer insulation film for display elements. Moreover, the interlayer insulation film for display elements formed from the said positive photosensitive resin composition is also suitably contained in this invention.

In the method of forming an interlayer insulating film for a display element of the present invention,

(1) process of forming the coating film of the said positive 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) heating the developed coating film.

According to the said formation method, in addition to the outstanding light resistance and heat resistance, the interlayer insulation film for display elements with high stability of a contact hole diameter can be formed. In addition, since the film thickness reduction amount of the unexposed part with respect to the developing time can be suppressed, the production process margin can be improved as a result, and the improvement of the yield can be achieved. Moreover, by forming a pattern by exposure, image development, and heating using photosensitivity, the interlayer insulation film for display elements which has a fine and sophisticated pattern can be formed easily. 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 electroluminescence display element.

As described above, the positive type photosensitive resin composition of the present invention can suppress the amount of 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. Can be provided. In addition, the stability of the contact hole diameter can be improved. Since the amount of film thickness reduction can be suppressed, the production process margin can be improved as a result, and the improvement of yield can be achieved. Moreover, by forming a pattern by exposure, image development, and heating using photosensitivity, the interlayer insulation film for display elements which has a fine and sophisticated pattern can be formed easily. 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 electroluminescence display element.

(Mode for carrying out the invention)

<Positive Photosensitive Resin Composition>

The positive photosensitive resin composition of this invention contains a [A] copolymer, a [B] compound, a [C] radical trapping agent, and a [D] solvent. Moreover, the said positive photosensitive resin composition may contain an [E] epoxy compound as a suitable component. In addition, as long as the effect of the present invention is not impaired, other optional components may be contained. Hereinafter, each component will be described in detail.

<[A] copolymer>

The copolymer (A) is a copolymer containing a structural unit (I) having a group represented by the formula (1) and a structural unit (II) having at least one (meth) acryloyloxy group. In addition, the [A] copolymer may contain the other structural unit in the range which does not impair the effect of this invention. In addition, the [A] copolymer may contain 2 or more types of each structural unit. Hereinafter, each structural unit is explained in full detail.

[Structural unit (I)]

Structural unit (I) has group represented by said formula (1). In the formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. However, some or all of the hydrogen atoms of the alkyl group, cycloalkyl group and aryl group may be substituted. In addition, R ¹ and R ² are not both hydrogen atoms. R ³ is a group represented by the alkyl group, cycloalkyl group, aralkyl group, aryl group, or -M (R ⁴⁾ _3. M is Si, Ge or Sn. R ⁴ is each independently an alkyl group. R ¹ and R ³ may be connected to form a cyclic ether structure. Provided that some or all of the hydrogen atoms of these groups represented by R &lt; ³ &gt; may be substituted.

Examples of the alkyl group represented by R ¹ and R ² include a linear or branched alkyl group having 1 to 30 carbon atoms. Examples of the linear or branched alkyl group having 1 to 30 carbon atoms include a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n- , straight-chain alkyl groups such as n-tetradecyl and n-octadecyl, branched groups such as i-propyl, i-butyl, Alkyl groups and the like.

Examples of the cycloalkyl group represented by R ¹ and R ² include a cycloalkyl group having 3 to 20 carbon atoms. In addition, the cycloalkyl group having 3 to 20 carbon atoms may be polycyclic. Examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a boronyl group, a norbornyl group and an adamantyl group.

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 monocyclic or monocyclic, or may be 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 substituent of the optionally substituted alkyl, cycloalkyl 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 cycloalkyl group (Such as phenyl and naphthyl), an alkoxy group (e.g., methyl, ethyl, n-propyl, i-propyl, i-propyl, An alkoxy group having 1 to 20 carbon atoms such as methoxy group, ethoxy group, propoxy group, n-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group and octyloxy group), an acyl group , An acyl group having 2 to 20 carbon atoms such as acetyl, propionyl, butyryl, and i-butyryl), an acyloxy group (e.g., acetoxy, Acyloxy group having 2 to 10 carbon atoms such as a t-amyloxy group, An alkoxycarbonyl group (for example, an alkoxycarbonyl group having 2 to 20 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group or a propoxycarbonyl group), a haloalkyl group (e.g., a methyl group, an ethyl group, an n- A straight chain alkyl group such as methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-dodecyl, an alkyl group such as a methyl group, an ethyl group, an isopropyl group, an n-propyl group, an isopropyl group, an isopropyl group, an isobutyl group, a butyl group, a neopentyl group, And a group in which a part or all of the hydrogen atoms of the cycloalkyl group such as a t-butyl group are substituted with a halogen atom), and the like.

As an alkyl group represented by said R <^3> and R <^4> , and a cycloalkyl group and an aryl group represented by R <^3> , the group illustrated by said R <^1> and R <^2> is applicable, for example. As the substituent of these groups, for example, the groups exemplified as substituents of the optionally substituted alkyl, cycloalkyl and aryl groups represented by R ¹ and R ² above may be applied. Examples of the aralkyl group represented by R &lt; ³ &gt; 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 which may be formed by connecting R ¹ and R ³ include a 2,2-oxetanediyl group, a 2,2-tetrahydrofuranyldihyl group, a 2-tetrahydropyranediyl group, And 2-dioxanediyl group.

Wherein R ¹ and R ^3, is said R ¹ and R ³ is preferably connected with and forms a cyclic ether structure. Moreover, it is preferable that the group represented by said formula (1) is group represented by said formula (1-1). By making the group represented by said Formula (1) into the said specific ring structure, hydrophobicity becomes high with respect to a developing solution, and the amount of film thickness reduction can be suppressed more.

As structural unit (I), the structural unit represented by following formula (1-2)-(1-4), etc. are mentioned, for example.

(In formula (1-2)-(1-4), R 'is a hydrogen atom or a methyl group; R <^1> , R <^2> and R <^3> are synonymous with said Formula (1).

As a monomer which gives the structural unit (I) represented by said Formula (1-2)-(1-4), for example, methacrylic acid 1-ethoxyethyl, methacrylic acid 1-methoxyethyl, methacrylic acid 1-n-butoxyethyl, methacrylic acid 1-isobutoxyethyl, methacrylic acid 1-t-butoxyethyl, methacrylic acid 1- (2-chloroethoxy) ethyl, methacrylic acid 1- (2- Ethylhexyloxy) ethyl, methacrylic acid 1-n-propoxyethyl, methacrylic acid 1-cyclohexyloxyethyl, methacrylic acid 1- (2-cyclohexylethoxy) ethyl, methacrylic acid 1-benzyloxy Ethyl, 2-tetrahydropyranyl methacrylate, 1-ethoxyethyl acrylate, 1-methoxyethyl acrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl acrylate, 1-t-butoxyethyl acrylate , Acrylic acid 1- (2-chloroethoxy) ethyl, acrylic acid 1- (2-ethylhexyloxy) ethyl, acrylic acid 1-n-propoxyethyl, acrylic acid 1-cyclohexyloxyethyl, acrylic acid 1- (2-cyclo Silethoxy) ethyl, acrylic acid 1-benzyloxyethyl, acrylic acid 2-tetrahydropyranyl, 2,3-di (1- (trimethylsilanyloxy) ethoxycarbonyl) -5-norbornene, 2,3 -Di (1- (trimethylgeryloxy) ethoxycarbonyl) -5-norbornene, 2,3-di (1-methoxyethoxycarbonyl) -5-norbornene, 2,3-di (1- (cyclohexyloxy) ethoxycarbonyl) -5-norbornene, 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- Benzyloxyethoxy Styrene and the like. These monomers may be used alone or in combination of two or more.

Among these, as a monomer which gives a structural unit (I), 1-n-butoxyethyl methacrylic acid and 2-tetrahydropyranyl methacrylate are preferable.

As the monomer giving the structural unit (I), commercially available monomers may be used, and those synthesized by known methods may be used. For example, the monomer which gives structural unit (I) represented by said Formula (1-2) can be synthesize | combined by making (meth) acrylic acid react with vinyl ether in presence of an acid catalyst, as shown to a following formula.

(In formula, R ', R <^1> and R <^3> is synonymous with said Formula (1-2); R <^21> and R <^22> is -CH (R <^21> ) (R <^22> ), It is said Formula (1) The same meaning as R ² in -2).

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

[Structural unit (II)]

As structural unit (II), if it has one or more (meth) acryloyloxy group, it will not specifically limit.

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

As a monomer (henceforth a "monomer (A1)") used for synthesis | combination of the [A1] copolymer, (meth) acrylic-acid hydroxyalkyl ester, (meth) acrylic-acid dihydroxyalkyl ester, (meth) acrylic acid (6 -Hydroxyhexanoyloxy) alkyl ester, etc. are mentioned.

As said (meth) acrylic-acid hydroxyalkyl ester, (meth) acrylic-acid 2-hydroxyethyl ester, (meth) acrylic-acid 3-hydroxypropyl ester, (meth) acrylic-acid 4-hydroxybutyl ester, etc. are mentioned, for example. have. As said (meth) acrylic-acid dihydroxyalkyl ester, it is (meth) acrylic-acid 2,3-dihydroxypropyl ester, (meth) acrylic-acid 1,3-dihydroxypropyl ester, (meth) acrylic acid 3,4, for example. -Dihydroxy butyl ester, etc. are mentioned. Examples of the (meth) acrylic acid (6-hydroxyhexanoyloxy) alkyl ester include, for example, (meth) acrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester and (meth) acrylic acid 3- (6-hydroxy) Hexanoyloxy) propyl ester etc. are mentioned.

Among these monomers (A1), acrylic acid 2-hydroxyethyl ester, acrylic acid 3-hydroxypropyl ester, acrylic acid 4-hydroxybutyl ester, and methacrylic acid 2-hydroxy from the viewpoint of copolymerization reactivity and reactivity with isocyanate compounds Ethyl ester, methacrylic acid 3-hydroxypropyl ester, methacrylic acid 4-hydroxybutyl ester, acrylic acid 2,3-dihydroxypropyl ester, methacrylic acid 2,3-dihydroxypropyl ester are preferable. These monomers may be used alone or in combination of two or more.

[A1] copolymer obtained as mentioned above may be used for the synthesis | combination of [A] copolymer as a polymerization reaction solution, and after separating [A1] copolymer from a solution once, it is provided for synthesis | combination of [A] copolymer. Also good.

As an unsaturated isocyanate compound, the isocyanate group containing derivative of (meth) acrylic acid, etc. are mentioned, for example. As an unsaturated isocyanate compound, 2- (meth) acryloyloxyethyl isocyanate, 4- (meth) acryloyloxy butyl isocyanate, 2- (2-isocyanate ethoxy) ethyl (meth) acrylic acid, 1,1, for example -(Bis (meth) acryloyloxymethyl) ethyl isocyanate etc. are mentioned. In addition, an unsaturated isocyanate compound can be used individually or in mixture of 2 or more types.

As a commercial item of an unsaturated isocyanate compound, it is a commercial item of 2-acryloyloxyethyl isocyanate, for example, As a commercial item of Karenz AOI (made by Showa Denko Co., Ltd.) and 2-methacryloyl oxyethyl isocyanate, As a commercial item of lens MOI (made by Showa Denko KK), 2- (2-isocyanate ethoxy) ethyl methacrylic acid, Kalenz MOI-EG (made by Showa Denko KK), 1,1- (bisacrylic) As a commercial item of royloxymethyl) ethyl isocyanate, Karenz BEI (made by Showa Denko KK) etc. is 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-isocyanate ethoxy) ethyl and 1,1- (bisacryloyloxymethyl) ethyl isocyanate are preferred.

The reaction of the [A1] copolymer with the unsaturated isocyanate compound is preferably unsaturated isocyanate with stirring in a solution of the [A1] copolymer containing a polymerization inhibitor, preferably at room temperature or under heating, in the presence of a suitable catalyst. It can carry out by adding a compound.

As said catalyst, dilauric-acid di-n-butyl tin (IV) etc. are mentioned, for example. As said polymerization inhibitor, p-methoxy phenol etc. are mentioned, for example.

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

As a synthesis | combining method of the [A2] copolymer, the method of superposing | polymerizing a carboxyl group-containing monomer (henceforth "monomer (A2)") etc. are mentioned from a viewpoint of material acquisition and synthesis | combination easy. .

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. Among these, (meth) acrylic acid is preferable.

As a compound which has a vinyl ether group and a (meth) acryloyloxy group, the compound etc. which are represented by following formula (4) are mentioned, for example.

(In formula (4), R <^6> is a hydrogen atom or a methyl group; R <^7> is a bivalent coupling group; R <^8> is a hydrogen atom or a monovalent organic group.).

As a bivalent coupling group represented by said R <^7> , a C2-C18 linear, branched or cyclic alkylene group, a C2-C20 alkoxyalkylene group, a C2-C8 halogenated alkylene group, a terminal hydroxyl group are mentioned, for example. Polyethyleneglycol frame | skeleton except for this, Polypropylene glycol frame | skeleton except terminal hydroxyl group, Polybutylene glycol frame | skeleton except terminal hydroxyl group, An aryl group, etc. are mentioned. As a monovalent organic group represented by said R <^8> , a C1-C10 linear, branched or cyclic alkyl group, the C6-C11 aromatic group etc. may be mentioned, for example.

As a compound which has the vinyl ether group and (meth) acryloyloxy group represented by said formula (4), it is (meth) acrylic acid 2-vinyloxyethyl, (meth) acrylic acid 3-vinyloxypropyl, (meth) acrylic acid, for example. 1-methyl-2-vinyloxyethyl, (meth) acrylic acid 2-vinyloxypropyl, (meth) acrylate 4-vinyloxybutyl, (meth) acrylic acid 1-methyl-3-vinyloxypropyl, (meth) acrylic acid 1- Vinyloxymethylpropyl, (meth) acrylic acid 2-methyl-3-vinyloxypropyl, (meth) acrylic acid 1,1-dimethyl-2-vinyloxyethyl, (meth) acrylic acid 3-vinyloxybutyl, (meth) acrylic acid 1 -Methyl-2-vinyloxypropyl, 2-vinyloxybutyl (meth) acrylate, 4-vinyloxycyclohexyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethylcyclo (meth) acrylate Hexylmethyl, (meth) acrylic acid 3-vinyloxymethylcyclohexylmethyl, (meth) acrylic acid 2-vinyloxymethyl Lohexylmethyl, (meth) acrylic acid p-vinyloxymethylphenylmethyl, (meth) acrylic acid m-vinyloxymethylphenylmethyl, (meth) acrylate o-vinyloxymethylphenylmethyl, (meth) acrylate 2- (vinyloxyethoxy) ethyl , (Meth) acrylic acid 2- (vinyloxyisopropoxy) ethyl, (meth) acrylic acid 2- (vinyloxyethoxy) propyl, (meth) acrylic acid 2- (vinyloxyethoxy) isopropyl, (meth) acrylic acid 2 -(Vinyloxyisopropoxy) propyl, (meth) acrylic acid 2- (vinyloxyisopropoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (vinyl Oxyethoxyisopropoxy) ethyl, (meth) acrylic acid 2- (vinyloxyisopropoxyethoxy) ethyl, (meth) acrylic acid 2- (vinyloxyisopropoxyisopropoxy) ethyl, (meth) acrylic acid 2- (Vinyloxyethoxyethoxy) propyl, (meth) acrylic acid 2- (vinyloxyethoxyisopropoxy) propyl, (meth) a 2- (vinyloxyisopropoxyethoxy) propyl acrylate, 2- (vinyloxyisopropoxyisopropoxy) propyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) isopropyl (meth) acrylate, ( Meta) acrylic acid 2- (vinyloxyethoxyisopropoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyisopropoxyethoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyisopropoxyisopropoxy) ) Isopropyl, (meth) acrylic acid 2- (vinyloxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (vinyloxyethoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (iso) Propenoxyethoxy) ethyl, (meth) acrylic acid 2- (isopropenoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (isopropenoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (isopropenoxyethoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid polyethylene glycol monovinyl ether, ( L), and the like of 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 combination of 2 or more types.

Among these compounds having a vinyl ether group and a (meth) acryloyloxy group, the compound represented by the formula (4) is preferable, and (meth) acrylic acid 2- (vinyloxyethoxy) ethyl is more preferable. Moreover, as a commercial item of 2- (vinyloxyethoxy) ethyl (meth) acrylate, for example, VEEA as 2- (vinyloxyethoxy) ethyl acrylate and VEEM as 2- (vinyloxyethoxy) ethyl methacrylate ( Nippon Shokubai Co., Ltd.) etc. are mentioned above.

The addition reaction of the copolymer [A2] with a compound having a vinyl ether group and a (meth) acryloyloxy group is not particularly limited and can be carried out by adding in the reaction system. In the said addition reaction, since the [A2] copolymer itself becomes a catalyst, reaction can be performed without a catalyst, but it is also possible to use a catalyst together.

 As another method for introducing the structural unit (II) into the copolymer [A], for example, a method of copolymerizing with the monomer to which the structural unit (I) is given using a polyfunctional (meth) acrylate as a monomer, etc. Can be mentioned.

As a polyfunctional (meth) acrylate, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, and tetraethylene Glycoldi (meth) acrylate, tricyclodecanediyldimethylenedi (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocy Anurate tri (meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tree (meth ) Acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl Cold di (meth) acrylate, the both terminal (meth) acrylic acid addition product of bisphenol A diglycidyl ether, 1, 4- butanediol di (meth) acrylate, 1, 6- hexanediol di (meth) acryl Latex, 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 dipentaerythritol 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, ethyl (Meth) of oxide 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 phenol novolac polyglycidyl ether ) Acrylates and the like. These monomers may be used alone or in combination of two or more.

As a commercial item of a polyfunctional (meth) acrylate, it is SA1002 (made by Mitsubishi Chemical Corporation), Viscoat 195, copper 230, copper 260, copper 215, copper 310, copper 214HP, East 295, East 300, East 360, East GPT, East 400, East 700, East 540, East 3000, East 3700 (above, manufactured by Osaka Yukikagaku Kogyo Co., Ltd.), Kayarad R-526, East HDDA, East NPGDA, East TPGDA, East MANDA, East R-551, East R-712, East R-604, East R-684, East PET-30, East GPO-303, East TMPTA, East THE-330, East DPHA, Copper DPHA-2H, Copper DPHA-2C, Copper DPHA-2I, Copper D-310, Copper D-330, Copper DPCA-20, Copper DPCA-30, Copper DPCA-60, Copper DPCA-120, Copper DN- 0075, copper DN-2475, copper T-1420, copper T-2020, copper T-2040, copper TPA-320, copper TPA-330, copper RP-1040, copper RP-2040, copper R-011, copper R- 300, copper R-205 (above, Nippon Kayaku Co., Ltd.), aronix (Aronix) M-210, copper M-220, copper M-233, copper M-240, copper M-215, copper M- 305, M-309, M-310, M-315, M-325, M-400, M M-6200, copper M-6400 (above, Toagosei Co., Ltd.), light acrylate BP-4EA, copper BP-4PA, copper BP-2EA, copper BP-2PA, copper DCP-A (above, Kyoiei Shakagaku Corporation, New Frontier BPE-4, East BR-42M, East GX-8345 (above, Daiichi Kogyo Seika Co., Ltd.), ASF-400 (Shin-Etsu Kagaku Co., Ltd.) Manufacture), Ripoxy SP-1506, East SP-1507, East SP-1509, East SP-4010, East SP-4060, East VR-77 (above, manufactured by Showa Kobunshi Co., Ltd.), NK Ester A-BPE-4 (made by Shin-Nakamura Kagaku Kogyo Co., Ltd.), etc. are mentioned.

Among 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 preferable. As a compound which has a 2 or more (meth) acryloyloxy group in a molecule | numerator, diethylene glycol di (meth) acrylate is more preferable. As a compound which has three or more (meth) acryloyloxy groups in a molecule | numerator, for example, a tri (meth) acrylate compound, a tetra (meth) acrylate compound, a penta (meth) acrylate compound, a hexa (meth) acrylate compound Etc. can be mentioned. Among the compounds having three or more (meth) acryloyloxy groups, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di Pentaerythritol penta (meth) acrylate and ditrimethylol propane tetra (meth) acrylate are preferable.

As content rate of the structural unit (II) in the [A] copolymer, 5 mol% or more and 60 mol% or less are preferable with respect to the total structural units contained in the [A] copolymer. When the copolymer (A) contains the structural unit (II) at the above specific content rate, the crosslinked structure between the molecular chains is further promoted, and as a result, the film thickness variation of the unexposed portion with respect to the development time is further enhanced. Not only can be further suppressed, but also the formation of an interlayer insulating film for a display element having better light resistance and heat resistance is made possible.

It is preferable that structural unit (II) has two or more (meth) acryloyloxy groups. When structural unit (II) has two or more (meth) acryloyloxy groups, in addition to the more favorable sensitivity and storage stability, the film thickness change of the unexposed part with respect to developing time can be further suppressed, and the shape of a contact hole Stability 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]

The copolymer (A) may contain other structural units other than the structural unit (I) and the structural unit (II) within a range that does not impair the effects of the present invention.

As a monomer which gives another structural unit, it is (meth) acrylic acid, (meth) acrylic-acid alkylester, (meth) acrylic-acid cycloalkylester, (meth) acrylic-acid aryl ester, (meth) acrylic-acid aralkyl ester, and unsaturated dika, for example. A main acid dialkyl ester, a vinyl aromatic compound, a conjugated diene compound, another unsaturated compound, etc. are mentioned.

As said (meth) acrylic-acid alkylester, For example, methyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, ( Meta) acrylate t-butyl, etc. are mentioned. As said (meth) acrylic-acid cycloalkyl ester, (meth) acrylic-acid cyclohexyl, (meth) acrylic-acid 2-methylcyclohexyl, (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl, (Meth) acrylic acid 2- (tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxy) ethyl, (meth) acrylic acid isobornyl, etc. are mentioned. As said (meth) acrylic-acid aryl ester, phenyl acrylate etc. are mentioned, for example. As (meth) acrylic-acid aralkyl ester, (meth) acrylic-acid benzyl etc. are mentioned, for example. As unsaturated dicarboxylic acid dialkyl ester, diethyl maleate, diethyl fumarate, etc. are mentioned, for example. As a vinyl aromatic compound, styrene, (alpha) -methylstyrene, etc. are mentioned, for example. As a conjugated diene compound, 1, 3- butadiene, isoprene, etc. are mentioned, for example. As another unsaturated compound, an acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, etc. are mentioned, for example. In addition, these monomers can use individual or 2 types or more.

Among these monomers, from the viewpoint of copolymerization reactivity, (meth) acrylic acid, methyl (meth) acrylate, n-butyl methacrylate, 2-methylglycidyl 2-methylglycidyl, benzyl methacrylate, methacrylic acid tricyclo [5.2 .1.0 ^2,6 ] decane-8-yl, styrene, p-methoxystyrene, 1,3-butadiene are preferred.

As polystyrene reduced weight average molecular weight (Mw) by gel permeation chromatography (GPC) of the copolymer (A), Preferably it is 2.0 * 10 <^3> -1.0 * 10 <^5> , More preferably, it is 5.0 * 10 <^3> -5.0 * 10. ⁴ By making Mw of a copolymer (A) into the said specific range, the sensitivity and alkali developability of the said positive photosensitive resin composition can be improved.

As polystyrene conversion number average molecular weight (Mn) by GPC of [A] copolymer, Preferably it is 2.0 * 10 <^3> -1.0 * 10 <^5> , More preferably, it is 5.0 * 10 <^3> -5.0 * 10 <^4> . By making Mn of a copolymer (A) into the said specific range, hardening reactivity at the time of hardening of the coating film of the said positive photosensitive resin composition can be improved.

As molecular weight distribution (Mw / Mn) of the [A] copolymer, Preferably it is 3.0 or less, More preferably, it is 2.6 or less. The developability of the interlayer insulation film for display elements obtained can be improved by making Mw / Mn of a copolymer (A) into 3.0 or less.

In addition, Mw and Mn of this specification were measured by GPC according to the following conditions.

Apparatus: GPC-101 (Showa Denko Corporation)

Column ： GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804

Mobile phase: Tetrahydrofuran

Column temperature: 40 degrees Celsius

Flow rate: 1.0 mL / min

Sample concentration: 1.0 mass%

Sample injection volume: 100μL

Detector: differential refractometer

Standard material: Monodisperse polystyrene

A copolymer (A) can be synthesize | combined by radical copolymerization etc. of the monomer which gives each said structural unit. As a solvent used for the polymerization reaction of the [A] copolymer, the solvent illustrated by the term of the solvent [D] which is a structural component of the said positive photosensitive resin composition mentioned later can be applied, for example.

As the polymerization initiator to be used in the polymerization reaction, those known as radical polymerization initiators can be used, and for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4- Azo compounds such as 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile) and 2,2'-azobis (methyl 2-methylpropionate); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxy pivalate, 1,1'-bis- (t-butylperoxy) cyclohexane; Hydrogen peroxide and the like.

In the polymerization reaction of the [A] copolymer, in order to adjust molecular weight, you may use a molecular weight modifier. As a molecular weight modifier, For example, 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; Azetidine derivatives such as dimethylzantogen sulfide and diisopropylzantogen disulfide; Terpinolene, (alpha) -methylstyrene dimer, etc. are mentioned.

&Lt; [B] Compound &gt;

The compound [B] is a compound that generates an acid by irradiation of radiation. As the radiation, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like can be used. When the positive photosensitive resin composition contains the compound [B], the positive photosensitive resin composition can exhibit positive radiation-sensitive characteristics. As a containing form in the said positive photosensitive resin composition of the compound (B), even if it is the form of the compound mentioned later, the form of the acid generator introduced as a part of the [A] copolymer or other polymer, or both forms, good.

It will not specifically limit, if it is a compound which has an oxime sulfonate group represented by said formula (2) as a compound [B]. In said formula (2), R <^5> is a linear, branched, or cyclic alkyl group or an aryl group. However, one part or all part of the hydrogen atom which the said alkyl group and aryl group have may be substituted.

As a linear, branched or cyclic alkyl group represented by said R <^5> , a C1-C10 linear or branched alkyl group is preferable. The linear or branched alkyl group having 1 to 10 carbon atoms may be substituted, and examples of the substituent include an alkoxy group having 1 to 10 carbon atoms and a bridged group such as a 7,7-dimethyl-2-oxonorbornyl group An alicyclic group including an alicyclic group, and the like. Moreover, as a preferable alicyclic group, it is a bicycloalkyl group. As an aryl group represented by said R <^5> , a C6-C11 aryl group is preferable and a phenyl group and a naphthyl group are more preferable. 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 oxime sulfonate group-containing compound represented by the above formula (2) include oxime sulfonate compounds represented by the following formula (3).

(In said formula (3), R <^9> is synonymous with R <^5> in said Formula (2); X is an alkyl group, an alkoxy group, or a halogen atom; m is an integer of 0-3; , When there are a plurality of X's, a plurality of X's may be the same or different).

The alkyl group which may 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 said Formula (3), the compound whose m is 1, X is a methyl group, and the substitution position of X is ortho is preferable.

As an oxime sulfonate compound represented by said (3), the compound etc. which are respectively represented by following formula (3-1)-(3-5) are mentioned, for example.

Compounds (3-1) to (3-5) each represent (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile and (5-octylsulfonyl Oxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (campsulsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5 -p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile, commercially available It can be obtained as.

As the compound (B), a compound represented by the formula (3) is preferable, and a compound represented by the formulas (3-1) to (3-5) available as a commercial item is more preferable.

As content of the compound [B] in the said positive photosensitive resin composition, when a compound [B] is a form of a compound, with respect to 100 mass parts of [A] copolymers, Preferably it is 0.1 mass part-10 mass parts. More preferably, they are 1 mass part-5 mass parts. By making content of a compound (B) into the said specific range, the interlayer insulation film for display elements excellent in light resistance and heat resistance can be formed, optimizing the sensitivity of the said positive photosensitive resin composition, and maintaining transparency.

Moreover, as a compound [B], in addition to the compound which has an oxime sulfonate group represented by said formula (2), onium salt, a sulfonimide compound, a halogen containing compound, diazomethane in the range which does not impair the effect of this invention. You may further contain a compound, a sulfone compound, a sulfonic acid ester compound, a carboxylic acid ester compound, and the like. In addition, these [B] compounds can be used individually or in combination of 2 or more types.

Examples of the onium salts include diphenyl iodonium salts, triphenylsulfonium salts, sulfonium salts, benzothiazonium salts, and tetrahydrothiophenium salts. Examples of the diphenyl iodonium salt include diphenyl iodonium tetrafluoroborate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroarsenate, diphenyl iodonium tri Diphenyl iodonium trifluoroacetate, diphenyl iodonium-p-toluene sulfonate, diphenyl iodonium butyl tris (2,6-difluorophenyl) borate, 4- Bis (4-t-butylphenyl) iodonium hexafluoroarsenate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium-p- (4-t-butylphenyl) iodonium camphorsulfonic acid, and the like. Examples of the triphenylsulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium- p-toluenesulfonate, triphenylsulfonium butyltris (2,6-difluorophenyl) borate, and the like. Examples of the sulfonium salt include an alkylsulfonium salt, a benzylsulfonium salt, a dibenzylsulfonium salt, and a substituted benzylsulfonium salt. Examples of the alkylsulfonium salt include 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenyl (Benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro 4-acetoxyphenylsulfonium hexafluoroantimonate, and the like. Examples of the benzylsulfonium salt include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexa 4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro- 4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, and the like. Examples of dibenzylsulfonium salts include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium Dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3- Methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate and the like. Examples of the substituted benzylsulfonium salt include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p -Chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl- Hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and the like. Examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p- 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, and the like can be used. . Examples of the tetrahydrothiophenium salt include 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen- 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- 1- (4-n-butoxy) -naphthalen-1-yl) tetrahydrothiophenium-1,1,2,2-tetrafluoro-2- (norbornan- (5-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoro (6-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) ethane sulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium- -1,1,2,2-tetrafluoroethanesulfonate, and the like.

Examples of the sulfonimide compounds include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (Camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphenylmaleimide, N- (4-methylphenylsulfonyloxy) (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- 2.2.1] hepto-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- (nonafluorobutanesulfonyloxy) bicyclo [2.2.1] hept- Dicarboxylic imide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (camphorsulfonyloxy) -7-oxabicyclo [2.2. 1] hept-5-ene-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [ 2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] Amide, N- (2-trifluoromethyl 2,6-dicarboxylic acid imide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept- 2,3-dicarboxylic imide, N (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] hepto-5- - (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptane- 5,6-oxy-2,3-dicarboxylic imide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane- 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) naphthyldicarboximide, N- (camphorsulfonyloxy) naphthyldicarboxylimide, N - (4-methylphenyl) (2-trifluoromethylphenylsulfonyloxy) naphthyldicarboxylic imide, N- (4-fluoro-4-fluorophenylsulfonyloxy) (Pentafluoroethylsulfonyloxy) naphthyldicarboxylic imide, N- (heptafluoropropylsulfonyloxy) naphthyldicarboxylimide, N- (nonafluoro (Butylsulfonyloxy) naphthyldicarbamylimide, N- (ethylsulfonyloxy) naphthyldicarboxyimide, N- (propylsulfonyloxy) naphthyldicarboxyimide, N- (Pentylsulfonyloxy) naphthyldicarboxylic imide, N- (hexylsulfonyloxy) naphthyldicarboximide, N- (heptylsulfonyloxy) naphthyldicarboxylic imide, N- Naphthyldicarboxyimide, and N- (nonylsulfonyloxy) naphthyldicarboxylimide.

As a halogen containing compound, a haloalkyl group containing hydrocarbon compound, a haloalkyl group containing heterocyclic compound, etc. are mentioned, for example.

As a diazomethane compound, bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexyl sulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolyl sulfide, for example) Ponyyl) diazomethane, bis (2, 4- xylylsulfonyl) diazomethane, bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyl diazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl (benzoyl) diazomethane, etc. are mentioned.

Examples of the sulfone compound include? -Ketosulfone compounds,? -Sulfonyl sulfone compounds, diaryl sulfone compounds, and the like.

As a sulfonic acid ester compound, an alkyl sulfonic acid ester, a haloalkyl sulfonic acid ester, an aryl sulfonic acid ester, an imino sulfonate, etc. are mentioned, for example.

Examples of the carbonic acid ester compound include carbonic acid o-nitrobenzyl ester and the like.

<[C] radical scavenger>

[C] The radical scavenger is a component capable of decomposing radicals generated by exposure or heating in the positive photosensitive resin composition or peroxide generated by oxidation, and preventing dissociation of bonds of polymer molecules. . As a result, as for the interlayer insulation film for display elements obtained from the said positive photosensitive resin composition, the said positive photosensitive resin composition can suppress the film thickness change amount more.

[C] As the radical trapping agent, for example, a compound having a hindered phenol structure, a compound having a hindered amine structure, a compound having an alkyl phosphite structure, a compound having a thioether structure, and the like can be given.

Examples of the compound having the hindered phenol structure include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -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), 2,6-di-t -Butyl-4-cresol, 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, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxy Oxyphenyl) propionate], 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6-xylyl) 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-triazin-2-ylamine) Phenol etc. are mentioned.

As a commercial item of the compound which has the said hindered phenol structure, For example, Adekastab (ADEKASTAB) AO-20, copper AO-30, copper AO-40, copper AO-50, copper AO-60, copper AO-70, Copper AO-80, Copper AO-330 (above, manufactured by ADEKA), Sumifierizer GM, Copper GS, Copper MDP-S, Copper BBM-S, Copper WX-R, GA-80 (Over) , Sumitomogagaku Co., Ltd.), IRGANOX 1010, East 1035, East 1076, East 1098, East 1135, East 1330, East 1726, East 1425WL, East 1520L, East 245, East 259, East 3114, East 565, IRGAMOD 295 (above, Chiba Japan Co., Ltd.), Yoshinox BHT, East BB, East 2246G, East 425, East 250, East 930, East SS, East TT, East 917, East 314 Corporation Corporation) etc. are mentioned.

Examples of the compound having the hindered amine structure include 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-butylmalonate, bis (1-acroyl-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-tetra Methyl-4-piperidylmethacrylate, 4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -1- [2- (3- (3,5 -Di-t-butyl-4-hydroxy Cyphenyl) 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, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4 -Butane tetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate, etc. are mentioned.

As a commercial item of the compound which has the said hindered amine structure, For example, adecas stab LA-52, copper LA57, copper LA-62, copper LA-67, copper LA-63P, copper LA-68LD, copper LA-77, East LA-82, East LA-87 (above, made by ADEKA), Sumerizer 9A (made by Sumitomo Kagaku Co., Ltd.), CHIMASSORB 119FL, East 2020FDL, East 944FDL, TINUVIN 622LD, East 144, East 765, East 770DF (made by Chiba Japan Co., Ltd.), etc. are mentioned.

Examples of the compound having an alkyl phosphite structure include tris (nonylphenyl) phosphite, tris (p-tert-octylphenyl) phosphite, and tris [2,4,6-tris (α-phenylethyl)] force. Fight, Tris (p-2-butenylphenyl) phosphite, bis (p-nonylphenyl) cyclohexylphosphite, tris (2,4-di-tert-butylphenyl) phosphite, di (2,4-di -tert-butylphenyl) pentaerythritoldiphosphite, 2,2'-methylenebis (4,6-di-t-butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus, distealyl penta Erythritol diphosphite, 4,4'-isopropylidenediphenolalkyl phosphite, tetratridecyl-4,4'-butylidene-bis (3-methyl-6-tert-butylphenol) diphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene phosphite, 2,6-di-tert-butyl-4-methylphenylphenylpentaerythritoldiphosphite, 2,6-tert- Butyl-4-methylphenylphenyl pentaerythritol diphosphite, 2,6-di- tert-butyl-4-ethylphenylstearylpentaerythritoldiphosphite, di (2,6-tert-butyl-4-methylphenyl) pentaerythritoldiphosphite, 2,6-di-tert-amyl-4-methylphenylphenyl Pentaerythritol diphosphite etc. are mentioned.

As a commercial item of the compound which has an alkyl phosphite structure, For example, adecastab PEP-4C, copper PEP-8, copper PEP-8W, copper PEP-24G, copper PEP-36, copper HP-10, copper 2112, copper 260, 522A, 1178, 1500, C, 135A, 3010, TPP (above, made by ADEKA), IRGAFOS 168 (manufactured by Chiba Japan).

Examples of the compound having the thioether structure include dilaurylthiodipropionate, ditridecylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate and pentaerythritol tetra Keith (3-laurylthiopropionate), pentaerythritol tetrakis (3-octadecylthiopropionate), pentaerythritol tetrakis (3-myristylthiopropionate), pentaerythritol tetrakis ( 3-stearylthiopropionate), etc. are mentioned.

As a commercial item of the compound which has a thioether structure, For example, Adecas Stab AO-412S, Copper AO-503 (above, made by ADEKA), Sumifier TPL-R, Copper TPM, Copper TPS, Copper TP-D, East MB (above, Sumitomo Kagaku Co., Ltd.), IRGANOXPS 800FD, East 802FD (above, Chiba Japan Co., Ltd.), DLTP, DSTP, DMTP, DTTP (above, AP Corporation) Can be mentioned.

Of these [C] radical scavengers, a compound having a hindered phenol structure is preferable, 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 preferred Do.

These compounds can be used individually or in combination of 2 or more types. In the positive photosensitive resin composition, the content of the radical scavenger [C] is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.2 parts by mass or more based on 100 parts by mass of the [A] copolymer. It is 5 mass parts or less. By making content of the [C] radical scavenger into the said specific range, the said positive photosensitive resin composition can suppress the film thickness change amount more.

<[D] solvent>

As the solvent [D], those which dissolve or disperse each component uniformly and which do not react with each component are suitably used. Examples of the solvent [D] include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, and propylene glycol monoalkyl ethers. Propionate, aromatic hydrocarbons, ketones, other esters, etc. are mentioned. These solvents may 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.

As the ethers, for example, tetrahydrofuran and the like can be mentioned.

As the glycol ether, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like can be given.

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

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

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

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

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 the aromatic hydrocarbons include toluene, xylene, and the like.

As ketones, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl- 2-pentanone, etc. are mentioned, for example.

Examples of other esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy- Hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3-hydroxypropionate, propyl 3-hydroxypropionate, propyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, Propyl methoxyacetate, propyl methoxy propionate, butyl 2-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetate, , Butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propoxyacetate Methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, Ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2- Methoxypropionate, methyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethyl propoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, Butyl, 3-propoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate and butyl 3-butoxypropionate.

Of 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, and diethylene glycol ethyl methyl ether and propylene are preferred. Glycol monomethyl ether acetate and methyl isobutyl ketone are more preferable. By selecting the said specific solvent, application | coating nonuniformity of a coating film surface can be suppressed, for example, when apply | coating a large sized board | substrate by a spinless method.

<[E] epoxy compound>

It is preferable that the said positive photosensitive resin composition further contains an [E] epoxy compound as a suitable component. When the positive photosensitive resin composition further contains the [E] epoxy compound, the light resistance and the heat resistance of the interlayer insulating film for display element formed of the positive photosensitive resin composition can be further improved.

The epoxy compound (E) 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 used in this specification is a concept containing an oxylanyl group (1, 2- epoxy structure) and an oxetanyl group (1, 3- epoxy structure).

As an [E] epoxy compound which has an oxiranyl group, it is, for example.

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;

1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Polyglycidyl ethers of polyhydric alcohols such as cidyl 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 novolak type epoxy resins;

Cresol novolak type epoxy resin;

Polyphenol type epoxy resins;

Cyclic aliphatic epoxy resins;

Diglycidyl esters of aliphatic long chain dibasic acids;

Glycidyl esters of higher fatty acids;

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 and bis {[1-ethyl (3-oxetanyl) ] Methyl} ether, bis (3-ethyl-3- oxetanylmethyl) ether, etc. are mentioned.

In addition, as a compound which has 2 or more 3, 4- epoxy cyclohexyl group in a molecule | numerator, for example, 3, 4- epoxy cyclohexyl methyl-3 ', 4'- epoxy cyclohexane carboxylate, 2- (3, 4 -Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methyl Cyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclo Pentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexanecarboxylate), lactone-modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane carboxylate, etc. are mentioned.

[E] As a commercial item of an epoxy compound, for example, EPICOAT 1001, copper 1002, copper 1003, copper 1004, copper 1007, copper 1009, copper 1010, copper 828 (above, manufactured by Japan Epoxy Resin Co., Ltd.) Bisphenol A epoxy resins, such as these; Bisphenol F-type epoxy resins such as Epicoat 807 (manufactured by Japan Epoxy Resin Co., Ltd.); Phenol novolak-type epoxy resins, such as Epicoat 152, 154, 157S65 (above, Japan Epoxy Resin Co., Ltd.), EPPN 201, 202 (above, Nippon Kayaku Co., Ltd.); Cresol novolac-type epoxy resins such as EOCN 102, 103S, 104S, 1010, 1025, 1027 (above, manufactured by Nippon Kayaku Co., Ltd.), and Epicoat 180S75 (manufactured by Japan Epoxy Resin Co., Ltd.);

Polyphenol type epoxy resins such as Epicoat 1032H60 and XY-4000 (above, manufactured by Japan Epoxy Resin Co., Ltd.); CY-175, East 177, East 179, Araldite CY-182, East 192, East 184 (above, manufactured by Chiba Specialty Chemicals Co., Ltd.), ERL-4234, East 4299, East 4221, 4206 (above, manufactured by UCC), Shodyne 509 (manufactured by Showa Denko Co., Ltd.), epiclon (EPICLON) 200, 400 (above, manufactured by Dainippon Inking Co., Ltd.), Epicoat Cyclic aliphatic epoxy resins such as 871, copper 872 (above, manufactured by Japan Epoxy Resin Co., Ltd.), ED-5661, copper 5662 (above, manufactured by Celanese Coating Co., Ltd.); EPORITE 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), Epiol TMP (manufactured by Nippon Yushi Co., Ltd.), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) And aliphatic polyglycidyl ethers such as methyl] benzene, bis {[1-ethyl (3-oxetanyl)] methyl} ether, and the like.

Among these [E] epoxy compounds, bisphenol A diglycidyl ether (polycondensate of 4,4'-isopropylidenediphenol and 1-chloro-2,3-epoxypropane), bisphenol F diglycidyl ether, Phenolic novolac 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 and 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate are preferred.

[E] The epoxy compound 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, it is 1 mass part-30 It is a mass part. By making content of the epoxy compound (E) 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 said [A]-[E] component, the said positive photosensitive resin composition is a [F] basic compound, a [G] surfactant, a quinonediazide compound etc. as needed in the range which does not impair the effect of this invention. You may contain other arbitrary components of. These other optional components may be used alone or in combination of two or more. Hereinafter, each component will be described in detail.

&Lt; [F] Basic compound &gt;

When the positive photosensitive resin composition contains the [F] basic compound, the diffusion length of the acid generated from the compound [B] by exposure can be appropriately controlled and the pattern developability can be improved. [F] The basic compound may be optionally selected from those used as chemical amplification registers, and examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and carboxylic acid quaternary ammonium salts. Can be.

Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di- Triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, and the like.

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

Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl- Benzimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxy Quinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4,3,0] , 1,8-diazabicyclo [5,3,0] -7-undecene, and the like.

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

Examples of the carbonic 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, and 0.005 mass part-0.2 mass part are more preferable. By setting the content of the [F] basic compound within the above-specified range, the pattern developability is further improved.

<[G] surfactant>

The surfactant (G) can further improve the coating film formability of the positive photosensitive resin composition. [G] As the surfactant, for example, a fluorine-based surfactant, a silicone-based surfactant, and the like can be mentioned. When the said positive photosensitive resin composition contains [G] surfactant, the surface smoothness of a coating film can be improved and the film thickness uniformity of the interlayer insulation film for display elements formed as a result can be improved more.

As a fluorine type surfactant, the compound which has a fluoroalkyl group and / or a fluoroalkylene group in at least one site | part of a terminal, a main chain, and a 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 glycoldi (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 glycoldi (1,1,2,2-tetrafluoro-n-butyl) ether, perfluoro-n-dode Sodium sulfonate, 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 fluoroalkyl phosphate, sodium fluoroalkyl carbonate, diglycerin tetrakis (fluoroalkyl Reoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, carboxylic acid fluoroalkyl ester, etc. Can be mentioned.

As a commercial item of a fluorine-type surfactant, BM-1000, BM-1100 (above, BM CHEMIE company make), Megapack (MEGAFAC) F142D, copper F172, copper F173, copper F183, copper F178, copper F191, copper F471 , F476 (above, Dai Nippon Inky Kagaku Kogyo Co., Ltd.), Fluorad (FLUORAD) FC-170C, East FC-171, East FC-430, East FC-431 (above, Sumitomo 3M Co., Ltd.) ), SURFLON S-112, S-113, S-131, S-141, S-145, S-382, Sufflon SC-101, S-102, S- 103, copper SC-104, copper SC-105, copper SC-106 (above, manufactured by Asahi Glass Co., Ltd.), F-top (EFTOP) EF301, copper EF303, copper EF352 (above, manufactured by Shin-Akita Chemical Co., Ltd.) ), FTERGENT FT-100, FT-110, FT-140A, FT-150, FT-250, FT-251, FT-300, FT-310, FT-400S And FTX-218 (manufactured by Neos Co., Ltd.).

As silicone type surfactant, for example, toray silicon DC3PA, copper DC7PA, copper SH11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH-190, copper SH-193, copper SZ-6032, copper SF-8428, Copper DC-57, Copper DC-190, SH 8400 FLUID (above, made by Toray Dow Corning Silicon), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 ( GE TOSHIBA SILICON CO., LTD., Organosiloxane polymer KP341 (made by Shin-Etsu Chemical Co., Ltd.), etc. are mentioned above.

As content of the [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, More preferably, it is 0.05 mass part or more It is 1 mass part or less. By making content of [G] surfactant into the said specific range, the film thickness uniformity of a coating film can be improved more.

<Quinonediazide compound>

The quinonediazide compound is a compound which generates carboxylic acid by irradiation of radiation. As the quinone diazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as &quot; mother nucleus &quot;) and 1,2-naphthoquinone diazidesulfonic acid halide can be used.

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

As trihydroxy benzophenone, 2, 3, 4- trihydroxy benzophenone, 2, 4, 6- trihydroxy benzophenone etc. are mentioned, for example. As tetrahydroxy benzophenone, it is 2,2 ', 4,4'- tetrahydroxy benzophenone, 2,3,4,3'- tetrahydroxy benzophenone, 2,3,4,4'-, for example. Tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, and the like. have. As pentahydroxy benzophenone, 2,3,4,2 ', 6'- pentahydroxy benzophenone etc. are mentioned, for example. As hexahydroxy benzophenone, it is 2,4,6,3 ', 4', 5'-hexahydroxy benzophenone, 3,4,5,3 ', 4', 5'-hexahydroxy benzo, for example. Phenone etc. are mentioned. Examples of the (polyhydroxyphenyl) alkane include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris -Tris (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, - [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'-spirobindene- , 6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavone and the like. As another mother nucleus, for example, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxycyclo, 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, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3 -Dihydroxy benzene is mentioned.

Among these 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 preferable.

As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable. As 1, 2- naphthoquinone diazide sulfonic-acid chloride, a 1, 2- naphthoquinone diazide- 4-sulfonic acid chloride, a 1, 2- naphthoquinone diazide-5-sulfonic acid chloride, etc. are mentioned, for example. . Of these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is preferable.

Condensates of a phenolic compound or an alcoholic compound with 1,2-naphthoquinonediazide sulfonic acid halide include 1,1,1-tri (p-hydroxyphenyl) ethane and 1,2-naphthoquinonediazide- Sulfonic acid chloride, a condensate of 4,4 '- [1- [4- [1- [4-hydroxyphenyl] -1- methylethyl] phenyl] ethylidene] bisphenol and 1,2- Diazide-5-sulfonic acid chloride is preferable.

In the condensation reaction of a phenolic compound or an alcoholic compound (mother nucleus) with 1,2-naphthoquinonediazidesulfonic acid halide, the amount of the phenolic compound or the alcoholic compound is preferably 30 to 85 mol% , And more preferably 50 mol% to 70 mol% of 1,2-naphthoquinonediazidesulfonic acid halide. Condensation reaction can be performed in accordance with a well-known method.

Examples of the quinone diazide compound include 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the mother nucleus is replaced with an amide bond, for example, 2,3,4-triaminobenzophenone-1, 2-naphthoquinonediazide-4-sulfonic acid amide and the like are also suitably used.

<Preparation method of positive type photosensitive resin composition>

The said positive photosensitive resin composition is melt | dissolved or disperse | distributed by mixing [A] copolymer, [B] compound, [C] radical scavenger, a suitable component, and other arbitrary components as needed with [D] solvent. It is prepared. For example, the positive photosensitive resin composition can be prepared by mixing each component in a predetermined ratio in the solvent [D].

&Lt; Method of forming interlayer insulating film for display element &gt;

The said positive photosensitive resin composition is suitable as a formation material of the interlayer insulation film for display elements. Moreover, the interlayer insulation film for display elements formed from the said positive photosensitive resin composition is also suitably contained in this invention.

In the method of forming an interlayer insulating film for a display element of the present invention,

(1) process of forming the coating film of the said positive 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) heating the developed coating film.

According to the said formation method, in addition to the outstanding light resistance and heat resistance, the interlayer insulation film for display elements with which the film thickness change of the unexposed part with respect to developing time is small can be formed. In addition, the stability of the contact hole diameter can be improved. In addition, since the film thickness reduction amount can be suppressed, the production process margin can be improved as a result, and an improvement in yield can be achieved. Moreover, by forming a pattern by exposure, image development, and heating using photosensitivity, the interlayer insulation film for display elements which has a fine and sophisticated pattern can be formed easily. 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 electroluminescence display element.

[Step (1)]

In this process, the said positive photosensitive resin composition is apply | coated on a board | substrate, and a coating film is formed. Preferably, the solvent is removed by prebaking the coated surface.

Examples of the substrate include glass, quartz, silicon, resin, and the like. Examples of the resin include ring-opening polymers of polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide and cyclic olefin, and hydrogenated products thereof. As conditions of prebaking, although it changes also with the kind of each component, a compounding ratio, etc., it can be made into about 70 to 120 degreeC and about 1 to 10 minutes.

[Step (2)]

In this step, at least part of the formed coating film is exposed to radiation. When exposing, it exposes normally through the photomask which has a predetermined pattern. As radiation used for exposure, the radiation in the range whose wavelength is 190 nm-450 nm is preferable, and the radiation which contains the ultraviolet-ray of 365 nm is more preferable. As an exposure amount, 500J / m <^2> -6,000J / m <^2> is preferable and is the value which measured the intensity | strength in the wavelength of 365nm of radiation with the illuminometer (OAI model356, OAI Optical Associates make), and 1,500J / m <^2> - 1,800 J / m ² is more preferable.

[Step (3)]

In this step, the coated film irradiated with the radiation is developed. By developing the coating film after exposure, an unnecessary part (irradiation part of radiation) is removed and a predetermined pattern is formed. As the developing solution used in the developing step, an alkaline aqueous solution is preferable. As an alkali, For example, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia; Quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and the like.

A suitable amount of water-soluble organic solvents and surfactants, such as methanol and ethanol, can also be used for aqueous alkali solution. As a density | concentration of alkali in aqueous alkali solution, 0.1 mass% or more and 5 mass% or less are preferable from a viewpoint of obtaining suitable developability. Examples of the developing method include a puddle method, a dipping method, a swing dipping method, a shower method, and the like. As image development time, although it changes with the composition of the said positive photosensitive resin composition, it is about 10 second-180 second. Following this development processing, for example, water washing is carried out for 30 seconds to 90 seconds, and then air is blown with compressed air or compressed nitrogen, for example, to form a desired pattern.

[Step (4)]

In this step, the developed coating film is heated. For heating, by heating a patterned thin film using heating apparatuses, such as a hotplate and oven, hardening reaction of a [A] copolymer can be accelerated | stimulated and hardened | cured material can be obtained. The heating temperature is, for example, about 120 ° C to 250 ° C. As heating time, although it changes with kinds of heating apparatus, it is about 5 to 30 minutes in a hotplate, and about 30 to 90 minutes in an oven, for example. Further, a step baking method in which two or more heating steps are performed may be used. In this manner, a patterned thin film corresponding to the target interlayer insulating film for a display element can be formed on the surface of the substrate. The use of the cured film is not limited to the interlayer insulating film for a display element, and can be used as a spacer or a protective film.

As a film thickness of the formed interlayer insulation film for display elements, Preferably it is 0.1 micrometer-8 micrometers, More preferably, they are 0.1 micrometer-6 micrometers.

(Example)

Hereinafter, the present invention will be described in detail on the basis of examples, but the present invention is not limitedly interpreted based on the description of this example.

&Lt; Synthesis of Component [A] &gt;

Synthesis Example 1

5 mass parts of 2,2'- azobisisobutylolnitrile and 250 mass parts of propylene glycol monomethyl ether acetates as a polymerization initiator are put into the flask provided with a cooling tube and the stirrer, and then the meta which gives structural unit (I) 55 parts by mass of 1-n-butoxyethyl methacrylic acid, 30 parts by mass of methacrylic acid 2-hydroxyethyl ester as the monomer (A1), and 10 parts by mass of methacrylic acid to give other structural units and 5 parts by mass of styrene After the mixture was replaced with nitrogen, the temperature of the solution was raised to 70 ° C. with gentle stirring, and the temperature was maintained for 5 hours to polymerize to obtain a [A1] copolymer solution having a solid content concentration of 28.8%. Mw of the obtained [A1] copolymer was 13,000.

12 mass parts of 2-methacryloyloxyethyl isocyanate (Karens MOI, Showa Denko KK make) and 0.1 mass part of 4-methoxy phenols as a polymerization inhibitor to a copolymer solution [A1] After the addition, the mixture was stirred at 40 ° C for 1 hour and further at 60 ° C for 2 hours to react. Progress of reaction with the isocyanate group derived from 2-methacryloyloxyethyl isocyanate and the hydroxyl group of the [A1] copolymer was confirmed by IR (infrared absorption) spectrum. After 1 hour at 40 ° C, the IR spectrum of the reaction solution after the reaction at 60 ° C for 2 hours was further measured, and the peak near 2,270 cm ⁻¹ derived from the isocyanate group of 2-methacryloyloxyethyl isocyanate is decreasing. In this regard, it was confirmed that the reaction was progressing. The copolymer (A-1) solution of 31.0% of solid content concentration was obtained. Mw of the copolymer (A-1) was 14,000. ^As a result of ¹³ C-NMR analysis, the content rate of each structural unit was structural unit (I): structural unit (II): other structural units = 42:31:27 (mol%). In addition, the ¹³ C-NMR analysis which calculated | required the content rate of each structural unit of a polymer used the nuclear magnetic resonance apparatus (The Nippon Denshi Corporation make, JNM-ECX400).

[Synthesis Example 2]

Instead of the 2-methacryloyloxyethyl isocyanate, 19 parts by mass of 1,1- (bisacryloyloxymethyl) ethyl isocyanate (Karens BEI, manufactured by Showa Denko KK) was added as an unsaturated isocyanate compound. Was obtained in the same manner as in Synthesis example 1 to obtain a copolymer (A-2) solution. Mw of the copolymer (A-2) was 15,000. Solid content concentration was 32.0 mass%. ^As a result of ¹³ C-NMR analysis, the content rate of each structural unit was structural unit (I): structural unit (II): other structural units = 42:30:28 (mol%).

[Synthesis Example 3]

540 parts by mass of diethylene glycol ethylmethyl ether was placed in a four-necked flask provided with a thermometer, a stirrer, and a cooling tube, and after nitrogen substitution, the temperature was raised to 90 ° C in an oil bath. 87 mass parts of methacrylic acid 2-tetrahydropyranyl which gives a structural unit (I), 90 mass parts of methacrylic acid as a monomer (A2), 40 mass parts of methyl methacrylates which give another structural unit, and superposition | polymerization 10 mass parts of 2,2'- azobisisobutyronitrile as an initiator were added, and it hold | maintained at the same temperature for 6 hours. Then, after heating up at 100 degreeC and maintaining temperature for 2 hours, the [A2] copolymer solution was obtained. 0.2 mass part of 4-methoxy phenols as a polymerization inhibitor are added to this copolymer solution, Then, 2- (vinyloxyethoxy) ethyl methacrylate as a compound which has a vinyl ether group and a (meth) acryloyloxy group Nippon Shokubai, VEEM) 128 mass parts was dripped uniformly by the dropping lot over 1 hour. After 12 hours of aging reaction, the reaction solution was cooled to room temperature to obtain a copolymer (A-3) solution. Mw of the copolymer (A-3) was 18,000. Solid content concentration was 37.5 mass%. ^As a result of ¹³ C-NMR analysis, the content rate of each structural unit was structural unit (I): structural unit (II): other structural units = 26:50:24 (mol%).

[Synthesis Example 4]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator and 200 parts by mass of diethylene glycol ethylmethyl ether were placed. Subsequently, 57 mass parts of methacrylic acid 2-tetrahydropyranyl which gives a structural unit (I), 8 mass parts of ethylene glycol dimethacrylates as a polyfunctional (meth) acrylate, and the methacryl which provides another structural unit 10 mass parts of acid, 20 mass parts of methyl methacrylates, and 3 mass parts of (alpha) -methylstyrene dimers as a molecular weight modifier were put, and it substituted by nitrogen, and stirred 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. Solid content concentration was 31.5 mass%. ^As a result of ¹³ C-NMR analysis, the content rate of each structural unit was structural unit (I): structural unit (II): other structural units = 48: 6: 46 (mol%).

Synthesis Example 5

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator and 200 parts by mass of diethylene glycol ethylmethyl ether were added. Subsequently, 30 mass parts of methacrylic acid 2-tetrahydropyranyl which gives a structural unit (I), 20 mass parts of ethylene glycol dimethacrylates as polyfunctional (meth) acrylate, and 50 mass of trimethylol propane trimethacrylates 3 mass parts of (alpha) -methylstyrene dimers as a molecular weight modifier were put, and nitrogen substitution was carried out, and 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. Solid content concentration was 33.5 mass%. ^As a result of ¹³ C-NMR analysis, the content rate of each structural unit was structural unit (I): structural unit (II) = 40:60 (mol%).

[Synthesis Example 6]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator and 400 parts by mass of diethylene glycol ethylmethyl ether were placed. Subsequently, 57 mass parts of methacrylic acid 2-tetrahydropyranyl which gives a structural unit (I), 8 mass parts of ethylene glycol dimethacrylates as a polyfunctional (meth) acrylate, and the methacryl which provides another structural unit 10 mass parts of acid, 20 mass parts of methyl methacrylates, and 3 mass parts of (alpha) -methylstyrene dimers as a molecular weight modifier were put, and it substituted by nitrogen, and stirred 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). Furthermore, 50 mass parts of trimethylol propane trimethacrylates as a polyfunctional (meth) acrylate was dripped at this copolymer solution over 1 hour by the dropping lot, and it stirred for 1 hour after that. Mw of the copolymer (A-6) was 25,000. Solid content concentration was 26.5 mass%. ^As a result of ¹³ C-NMR analysis, the content rate of each structural unit was structural unit (I): structural unit (II): other structural units = 48: 6: 46 (mol%).

[Synthesis Example 7]

 In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethylmethyl ether were placed. Subsequently, 40 parts by mass of 1-ethoxyethyl methacrylate giving the structural unit (I), 5 parts by mass of methacrylic acid, 5 parts by mass of styrene and 2-hydroxyethyl methacrylate 10 giving the other structural units. After mass part and 40 mass parts of glycidyl methacrylates were added and nitrogen-substituted, 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 a copolymer (CS-1). Mw of the copolymer (CS-1) was 10,000. Solid content concentration was 32.1 mass%.

<Synthesis of [E] epoxy compound>

[Synthesis Example 8]

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol ethylmethyl ether were placed. Subsequently, 15 parts by mass of methacrylic acid, 20 parts by mass of methyl methacrylate, 30 parts by mass of benzyl methacrylate, 5 parts by mass of styrene, and 30 parts by mass of glycidyl methacrylate were added and replaced with nitrogen, followed by gentle stirring. The solution containing the copolymer (E-4) was obtained by raising the temperature of the solution to 70 ° C and maintaining the temperature for 5 hours to polymerize. Mw of the copolymer (E-4) was 8,000. Solid content concentration was 32.3 mass%.

<Preparation of positive type photosensitive resin composition>

Hereinafter, the component used for preparation of the positive photosensitive resin composition of an Example and a comparative example is explained in full detail.

Component [B]

B-1: (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (made by Chiba Specialty Chemicals, IRGACURE PAG 103)

B-2: (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (made by Chiba Specialty Chemicals, IRGACURE PAG 108)

B-3: (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (made by Chiba Specialty Chemicals, IRGACURE PAG 121)

B-4: (Campersulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl) acetonitrile (made by Chiba Specialty Chemicals, CGI1380)

B-5: (5-octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile (made by Chiba Specialty Chemicals, CGI725)

b-1 (quinonediazide compound): 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol), 1, Condensate with 2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol)

[C] radical scavengers

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, Adecastab LA-57)

C-4 ： distealyl pentaerythritol diphosphite (manufactured by ADEKA, ADEKA STAB PEP-8)

C-5: pentaerythritol tetrakis (3-lauryl thiopropionate) (made 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 compounds

E-1 ： Phenolic novolac-type epoxy resin

E-2: bisphenol A diglycidyl ether (polycondensation product of 4,4'-isopropylidenediphenol and 1-chloro-2,3-epoxypropane)

E-3: Bis (3-ethyl-3- oxetanylmethyl) ether

E-5: 3, 4- epoxycyclohexyl methyl-3 ', 4'- epoxy cyclohexane carboxylate

[F] Basic compound

F-1 ： 4-dimethylaminopyridine

F-2: 4-methylimidazole

[G] surfactants

G-1: Silicone type surfactant (Toray Dow Corning Silicone Co., Ltd. make, SH 8400 FLUID)

G-2: Fluorine type surfactant (Neosu Co., Ltd. make-up FTX-218)

Example 1

[D] The compound [B] in the solution (amount corresponding to 100 parts by mass (solid content) of (A-1)) containing (A-1) as a copolymer in (D-1) as a solvent. (B-1) 3.0 parts by mass, (C-1) 0.5 parts by mass as the [C] radical scavenger, (E-1) 5.0 parts by mass as the [E] epoxy compound, and (G) as the surfactant -1) Positive type photosensitive resin composition was prepared by mixing 0.20 mass part and filtering by the membrane filter of 0.2 micrometer of pore diameters.

[Examples 2 to 10 and Comparative Examples 1 and 2]

Except having made the kind and compounding quantity of each component as Table 1, it operated like Example 1, and prepared each positive type photosensitive resin composition. In addition, "-" in Table 1 shows that the corresponding component was not used. In addition, the value of the [D] solvent used in Table 1 is a mass ratio when it is set as a mixed solvent.

<Evaluation>

The following evaluation was performed using each prepared positive photosensitive resin composition. The results are shown together in Table 1.

[Sensitivity (J / m ² )]

Hexamethyldisilazane (HMDS) was apply | coated on 550x650 mm chromium film-forming glass, and it heated at 60 degreeC for 1 minute. On the chromium film-forming glass after this HMDS process, each positive type photosensitive resin composition was apply | coated using a slit die coater (TR632105-CL, the Tokyo Corporation make), The arrival pressure was set to 100 Pa, and a solvent is made under vacuum. After removal, the film was further prebaked at 90 ° C. for 2 minutes to form a coating film having a film thickness of 4.0 μm. Subsequently, using an exposure machine (manufactured by Canon Co., Ltd., MPA-600FA, ghi-ray mixture), through a mask having a pattern of a contact hole of 10 µm, the exposure dose was varied with respect to the coating film at a proxy gap of 10 µm. Investigated. Then, it developed at 25 degreeC for 70 second in the 0.5 mass% tetramethylammonium hydroxide aqueous solution. Subsequently, flowing water wash | cleaned with ultrapure water and drying after that, the pattern was formed on the glass substrate after the HMDS process. At this time, the exposure amount closest to the contact hole diameter of 10 micrometers was made into the radiation sensitivity. It was judged that the sensitivity was good when this value was 500 (J / m ² ) or less.

[Appearance of Coating Film]

Each positive photosensitive resin composition prepared on a 550 × 650 mm chromium film-forming glass was applied using a slit die coater (TR632105-CL, manufactured by Tokyo Okagyo Co., Ltd.), dried under reduced pressure to 0.5 Torr, and then 100 on a hot plate. The film was prebaked at 2 ° C. for 2 minutes to form a coating film and exposed at an exposure dose of 2,000 J / m ² to form a film having a film thickness of 4 μm from the upper surface of the chromium film-forming glass. Under a sodium lamp, the appearance of this coating film was visually observed. At this time, streaks (one or a plurality of straight spots occurring in the coating direction or the direction intersecting with them), mist spots (cloud spots), pin marks (spots formed on the substrate support pin) in the entire coating film Of the appearance of stains). The case where almost none of these stains were seen was "A" (good judgment), and the case where it was seen a little was "B" (it judged to be a little bad), and the case where it was clearly seen was made into "C" (judged bad).

[Film thickness change rate (%)]

HMDS was apply | coated on the alkali free glass substrate, and it heated for 3 minutes. After applying each positive type photosensitive resin composition using a spinner, it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the coating film of 4.1 micrometers in film thickness. The exposure gap was set to 30 micrometers through the mask of a contact hole pattern, and the exposure was performed similarly to the evaluation of the said sensitivity, and the obtained coating film was exposed. Then, image development was performed by 23 degreeC and the puddle method in 0.5 mass% tetramethylammonium hydroxide aqueous solution. At this time, the developing time was changed to 50 seconds, 70 seconds, and 90 seconds. After that, it was rinsed with ultrapure water for 8 seconds. It measured about the film thickness of the unexposed part after image development, and computed the film thickness change rate (%) from this value and a following formula.

Film thickness change rate after development (%) = (film thickness after development / film thickness before development) × 100

Also in the case where the developing time was changed to 50 seconds, 70 seconds, and 90 seconds, when the film thickness change rate was 90% or more, the amount of decrease in the film thickness with respect to the developing time could be suppressed, and it was judged to be good.

[Shape Stability of Contact Hole (µm)]

It carried out similarly to the evaluation of the said film thickness change rate, the coating film was formed on the alkali free glass substrate, and the prebaking temperature was changed to 80 degreeC, 90 degreeC, and 100 degreeC. Thereafter, except that the developing time was set to 90 seconds, the mask size was exposed and developed in the same manner as in the evaluation of the film thickness change rate through a mask of a contact hole having a 10 µm thickness to form a contact hole pattern. Then, the contact hole pattern formed by each prebaking temperature condition which post-baked in the clean oven at 220 degreeC for 45 minutes was observed with SEM (scanning electron microscope), and the shape and the size of the contact hole pattern were measured. . When the size of a contact hole pattern was 9.0 micrometers-11.0 micrometers, it was judged that the shape stability (micrometer) of the contact hole with respect to the change of prebaking temperature was favorable.

[Light Resistance (%)]

It carried out similarly to the evaluation of the said film thickness change rate, and carried out the coating film on the alkali free glass substrate, performed for 2 minutes with the prebaking temperature as 90 degreeC, and formed the coating film with a film thickness of 3.0 micrometers. Thereafter, no exposure was performed, and development was performed at 25 ° C. for 70 seconds in a 0.5% by mass aqueous tetramethylammonium hydroxide solution. Then, postbaking was performed in the clean oven for 45 minutes at 220 degreeC. The light transmittance in 400 nm of the obtained cured film was measured (T1). Then, it irradiated for 70 hours with the Xe lamp (roughness 180W / m <^2> ). The light transmittance at 400 nm of the cured film after irradiation was measured (T2). From these values and the following formula, the light transmittance change rate (%) before and after irradiation was computed by the following formula, and this was made into light resistance (%).

Light resistance (%) = {(T1-T2) / T1｝ × 100

When the value was 5% or less, it was judged that light resistance was good.

[Heat resistance (%)]

The TGA (thermogravimetric analysis) of the cured film after post-baking obtained by the said light resistance evaluation was performed using the Q5000SA made from TA Instruments company. The temperature was raised from room temperature to 250 ° C. for 20 minutes, and then maintained at 250 ° C. for 10 minutes to measure weight loss. The weight at room temperature before measurement was made into 100%, the weight loss after measurement was measured, and it was set as heat resistance (%). When the value was 5% or less, it was judged that the weight loss by heat was small and heat resistance was favorable.

[Storage stability (%)]

It operated similarly to the said film thickness change rate, the coating film of each positive type photosensitive resin composition immediately after preparation was formed, and the film thickness was measured (it is called "film thickness immediately after preparation" in the following formula). In addition, the film thickness of the cured film formed similarly after 14 days after preserve | saving each positive type photosensitive resin composition at 30 degreeC for 14 days was measured (it is called "film thickness after 14 days" in the following formula). The film thickness increase rate (%) was computed from the following formula, and it was set as storage stability (%).

Storage stability (%) = ｛(film thickness immediately after preparation-14 days) / film thickness immediately after preparation｝ × 100

When the value was 5% or less, it was judged that the storage stability was good.

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

In addition to the good sensitivity and storage stability, the positive photosensitive resin composition of the present invention can suppress the amount of change in the film thickness of the unexposed part with respect to the development time, and can provide an interlayer insulating film for display elements having excellent light resistance and heat resistance. . In addition, the stability of the contact hole diameter can be improved. 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. Moreover, by forming a pattern by exposure, image development, and heating using photosensitivity, the interlayer insulation film for display elements which has a fine and sophisticated pattern can be formed easily. 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 electroluminescence display element.

Claims (10)

(A) Copolymer containing structural unit (I) which has group represented by following formula (1), and structural unit (II) which has 1 or more (meth) acryloyloxy group,
[B] a compound having an oxime sulfonate group represented by the following formula (2),
[C] radical scavengers, and
[D] Solvent
Positive photosensitive resin composition containing:

(In formula (1), R <^1> and R <^2> is a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group each independently; and R <^1> and R <^2> are not all 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 ; M is Si, Ge, or Sn; R ⁴ is each independently an alkyl group; and R ¹ and R ³ May be linked to form a cyclic ether structure);

(In formula (2), R <^5> is a linear, branched, or cyclic alkyl group or an aryl group.). The method of claim 1,
In the group represented by the formula (1), the positive photosensitive resin composition in which the R ¹ and R ³ are connected to form a cyclic ether structure. The method of claim 1,
Positive type photosensitive resin composition whose group represented by said formula (1) is group represented by following formula (1-1).

4. The method according to any one of claims 1 to 3,
Positive type photosensitive resin composition whose content rate of structural unit (II) in (A) copolymer is 5 mol% or more and 60 mol% or less. 4. The method according to any one of claims 1 to 3,
Positive type photosensitive resin composition in which a structural unit (II) has two or more (meth) acryloyloxy groups. 4. The method according to any one of claims 1 to 3,
(D) Positive type photosensitive resin composition whose solvent is at least 1 sort (s) of solvent chosen from the group which consists of ketones, ethylene glycol monoalkyl ethers, diethylene glycol alkyl ethers, and propylene glycol monoalkyl ether acetates. 4. The method according to any one of claims 1 to 3,
[E] Positive type photosensitive resin composition which further contains the compound which has 2 or more epoxy groups in a molecule | numerator. 4. The method according to any one of claims 1 to 3,
Positive photosensitive resin composition used for formation of the interlayer insulation film for display elements. (1) Process of forming the coating film of positive type 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 step of developing the coating film irradiated with the radiation, and
(4) a step of heating the developed coating film
Of the interlayer insulating film for a display element. The interlayer insulation film for display elements formed from the positive photosensitive resin composition of Claim 8.