JP5949094B2 - Positive radiation-sensitive composition, interlayer insulating film for display element, and method for forming the same - Google Patents

Description

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

  The display element is generally provided with a display element interlayer insulating film for the purpose of insulating between wirings arranged in layers. As a material for forming an interlayer insulating film for a display element, the number of processes for obtaining a necessary pattern shape is small, and since a high level of flatness is required for the obtained interlayer insulating film for a display element, a radiation-sensitive resin composition Is widely used. Such a radiation sensitive resin composition is required to have good sensitivity, and the interlayer insulating film for display elements has excellent surface hardness, solvent resistance, heat resistance, voltage holding ratio, etc. in addition to the above flatness. Desired.

  As such a radiation sensitive resin composition, a composition containing a cross-linking agent, an acid generator and an alkali-soluble resin is known (see JP 2004-4669 A). The alkali-soluble resin has a protecting group (a group that is insoluble or hardly soluble in an alkaline aqueous solution and can be dissociated by the action of an acid), and becomes soluble or easily soluble in an alkaline aqueous solution after the protective group is dissociated. Refers to resin. As another radiation sensitive resin composition, a radiation sensitive resin composition containing an acetal structure or a ketal structure and an epoxy group-containing resin and an acid generator has been proposed (Japanese Patent Laid-Open No. 2004-264623). (See the publication).

  However, the conventional radiation-sensitive resin composition has an inconvenience that a fine and fine pattern cannot be easily formed because of insufficient radiation sensitivity.

JP 2004-4669 A JP 2004-264623 A

  The present invention has been made based on the circumstances as described above, and an object thereof is to provide an interlayer insulating film for a display element having higher sensitivity and excellent surface hardness, solvent resistance, heat resistance and voltage holding ratio. It is to provide a positive radiation sensitive composition that can be formed, an interlayer insulating film for a display element formed using the composition, and a method for forming the interlayer insulating film.

（式（１）中、Ｒ^１は、水素原子又はメチル基である。Ｒ^２は、炭素数６〜３０のアルキル基、アルケニル基、アルキニル基若しくはアシロキシアルキル基又は炭素数４〜３０の橋かけ環式炭化水素基である。但し、上記アルキル基、アルケニル基、アルキニル基、アシロキシアルキル基及び橋かけ環式炭化水素基が有する水素原子の一部は、水酸基又はカルボキシル基で置換されていてもよい。） The invention made to solve the above problems is
[A] A polymer having a structural unit (I) containing an acid dissociable group, a structural unit (II) containing a polymerizable group, and a structural unit (III) represented by the following formula (1) (hereinafter referred to as “[A ] [Polymer]], and [B] A positive radiation sensitive composition containing a radiation sensitive acid generator.

(In Formula (1), R ¹ is a hydrogen atom or a methyl group. R ² is an alkyl group having 6 to 30 carbon atoms, an alkenyl group, an alkynyl group, an acyloxyalkyl group, or a bridge having 4 to 30 carbon atoms. A cyclic cyclic hydrocarbon group, provided that a part of the hydrogen atoms of the alkyl group, alkenyl group, alkynyl group, acyloxyalkyl group and bridged cyclic hydrocarbon group is substituted with a hydroxyl group or a carboxyl group. May be.)

In the positive radiation sensitive composition, the [A] polymer has a structural unit (III) containing a group represented by R ² , so that the flexibility before curing is increased, and as a result, it is generated during exposure. The diffusion of the acid is promoted, and the sensitivity can be further improved. In addition, the positive radiation sensitive composition has sufficient surface hardness, solvent resistance, heat resistance, and voltage holding ratio because the polymer [A] has a structural unit (II) containing a polymerizable group. A cured film such as an interlayer insulating film for display elements can be formed.

  The positive radiation-sensitive composition preferably further contains a compound having a molecular weight of 1,000 or less (hereinafter also referred to as “[C] compound”) containing one or more [C] (meth) acryloyl groups. The positive radiation-sensitive composition can further form a cured film having further improved surface hardness, solvent resistance, heat resistance, and voltage holding ratio by further containing the [C] compound.

（式（２）中、Ｒ^３及びＲ^４は、それぞれ独立して、水素原子、アルキル基、脂環式炭化水素基又はアリール基である。但し、これらのアルキル基、脂環式炭化水素基又はアリール基が有する水素原子の一部又は全部は置換されていてもよい。また、Ｒ^３及びＲ^４が共に水素原子である場合はない。Ｒ^５は、アルキル基、脂環式炭化水素基、アラルキル基、アリール基又は−Ｍ（Ｒ^６）_３で表される基である。Ｍは、Ｓｉ、Ｇｅ又はＳｎである。Ｒ^６は、アルキル基である。但し、Ｒ^５のアルキル基、脂環式炭化水素基、アラルキル基及びアリール基並びにＲ^６のアルキル基が有する水素原子の一部又は全部は置換されていてもよい。Ｒ^３とＲ^５とが互いに結合して、Ｒ^３が結合している炭素原子及びＲ^５が結合している酸素原子と共に環状エーテル構造を形成してもよい。） The acid dissociable group in the structural unit (I) is preferably represented by the following formula (2).

(In Formula (2), R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group or an aryl group, provided that these alkyl groups and alicyclic hydrocarbon groups are Alternatively, some or all of the hydrogen atoms of the aryl group may be substituted, and R ³ and R ⁴ are not both hydrogen atoms, and R ⁵ is an alkyl group or an alicyclic hydrocarbon group. , An aralkyl group, an aryl group, or a group represented by —M (R ⁶ ) _3. M is Si, Ge, or Sn, R ⁶ is an alkyl group, provided that an alkyl group of R ⁵ , Some or all of the hydrogen atoms of the alicyclic hydrocarbon group, the aralkyl group, the aryl group, and the alkyl group of R ⁶ may be substituted, and R ³ and R ⁵ are bonded to each other, and R ³ is oxygen atoms carbon atoms and R ⁵ bonded to that is bonded Together may form a cyclic ether structure.)

  The acid dissociable group represented by the above formula (2) has a structure that is easily dissociated by the action of an acid generated from the [B] radiation sensitive acid generator. Therefore, the positive radiation-sensitive composition can further improve sensitivity by containing such an acid dissociable group [A] polymer, and easily form a fine and elaborate pattern. can do.

  The polymerizable group in the structural unit (II) is preferably an epoxy group. [A] When the polymer contains an epoxy group as a polymerizable group, a cured film such as an interlayer insulating film for display elements formed from the positive radiation-sensitive composition has surface hardness, solvent resistance, and heat resistance. In addition, the voltage holding ratio can be further improved. Here, the epoxy group is a concept including an oxiranyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure).

  [A] The content of the structural unit (III) in the polymer is preferably 3% by mass or more and 50% by mass or less. Thus, by making the content rate of the structural unit (III) in a [A] polymer into the said range, the spreading | diffusion of an acid is accelerated | stimulated more and a sensitivity can be improved more.

  [C] The compound is preferably a compound having a skeleton derived from a diol structure having 2 to 12 carbon atoms, a skeleton derived from trimethylolpropane, a skeleton derived from pentaerythritol, or a skeleton derived from dipentaerythritol. Thus, by containing the specific compound as the [C] compound, the surface hardness, solvent resistance, heat resistance and voltage holding ratio of a cured film such as an interlayer insulating film for display elements to be formed are further improved. be able to.

  [C] The content of the compound is preferably 1% by mass or more and 50% by mass or less in terms of solid content. The positive-type radiation-sensitive composition has a [C] compound content in the above range, whereby the surface hardness, solvent resistance, heat resistance, and voltage of a cured film such as an interlayer insulating film for display elements to be formed. The retention rate can be made excellent.

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

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

  According to the formation method, an interlayer insulating film for a display element that is excellent in surface hardness, solvent resistance, heat resistance, and voltage holding ratio can be formed. Moreover, the interlayer insulation film for display elements which has a fine and elaborate pattern can be easily formed by using the said positive type radiation sensitive composition excellent in a sensitivity. Therefore, the formed interlayer insulation film for display elements can be used suitably for display elements, such as a liquid crystal display element and an organic EL display element.

  The “radiation” of the “positive radiation-sensitive composition” in the present specification is a concept including visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams and the like.

  As described above, since the positive radiation sensitive composition of the present invention is excellent in sensitivity, an interlayer insulating film for a display element having a fine and elaborate pattern can be easily formed. In addition, the positive radiation sensitive composition can form an interlayer insulating film for a display element that is excellent in surface hardness, solvent resistance, heat resistance, and voltage holding ratio. Therefore, the positive radiation sensitive composition is suitable as a material for forming an interlayer insulating film for display elements such as liquid crystal display elements and organic EL display elements.

<Positive radiation sensitive composition>
The positive radiation sensitive composition of the present invention contains a [A] polymer and a [B] radiation sensitive acid generator as essential components, and a [C] compound as preferred components. Moreover, the said positive type radiation sensitive composition may contain another arbitrary component in the range which does not impair the effect of this invention. Hereinafter, each component will be described in detail.

<[A] polymer>
[A] The polymer is a polymer having a structural unit (I) containing an acid dissociable group, a structural unit (II) containing a polymerizable group, and a structural unit (III) represented by the above formula (1). . [A] The polymer may contain other structural units as long as the effects of the present invention are not impaired. In addition, the [A] polymer may have 2 or more types of each structural unit. Hereinafter, each structural unit will be described in detail.

[Structural unit (I)]
The structural unit (I) is a structural unit containing an acid dissociable group. This acid-dissociable group is dissociated by the action of an acid generated from the [B] radiation-sensitive acid generator during exposure to generate a polar group, so that the [A] polymer that is insoluble or hardly soluble in an aqueous alkali solution Becomes soluble in an alkaline aqueous solution. The said positive type radiation sensitive composition can be equipped with a favorable sensitivity because the [A] polymer has such a structural unit (I).

The structural unit (I) is not particularly limited as long as it is a structural unit containing an acid-dissociable group, but from the viewpoint of being easily dissociated by an acid, the structural unit containing an acid-dissociable group represented by the above formula (2) It is preferable that In the formula (2), R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group or an aryl group. However, some or all of the hydrogen atoms of these alkyl groups, alicyclic hydrocarbon groups, or aryl groups may be substituted. Moreover, there is no case where R ³ and R ⁴ are both hydrogen atoms. R ⁵ is an alkyl group, an alicyclic hydrocarbon group, an aralkyl group, an aryl group, or a group represented by —M (R ⁶ ) ₃ . M is Si, Ge, or Sn. R ⁶ is an alkyl group. However, some or all of the hydrogen atoms of the alkyl group of R ⁵ , the alicyclic hydrocarbon group, the aralkyl group, the aryl group, and the alkyl group of R ⁶ may be substituted. R ³ and R ⁵ may be linked to form a cyclic ether structure.

Examples of the alicyclic hydrocarbon group represented by R ³ and R ⁴ include an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Moreover, this C3-C20 alicyclic hydrocarbon group may be polycyclic. Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a bornyl group, a norbornyl group, and an adamantyl group.

Examples of the aryl group represented by R ³ and R ⁴ include an aryl group having 6 to 14 carbon atoms. The aryl group having 6 to 14 carbon atoms may be a single ring, a structure in which single rings are connected, or a condensed ring. Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group.

Examples of the substituent of the optionally substituted alkyl group, alicyclic hydrocarbon group and aryl group represented by R ³ and R ⁴ include a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, and a carbonyl group. Group, alicyclic hydrocarbon group (for example, cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl, cyclooctyl, bornyl group, norbornyl group, adamantyl group, etc.), aryl group (for example, phenyl group, naphthyl group, etc.), alkoxy A group (for example, an alkoxy group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group), an acyl group (for example, , An acetyl group, a propionyl group, a butyryl group, an i-butyryl group and the like having 2 to 20 carbon atoms A siloxy group), an acyloxy group (for example, an acetoxy group, an ethylyloxy group, a butyryloxy group, a t-butyryloxy group, a t-amylyloxy group, etc., an acyloxy group having 2 to 10 carbon atoms), an alkoxycarbonyl group (for example, a methoxycarbonyl group) C2-C20 alkoxycarbonyl groups such as ethoxycarbonyl group and propoxycarbonyl group), haloalkyl groups (for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group) , N-octyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group and the like linear alkyl group, i-propyl group, i-butyl group, t-butyl group, neopentyl group, 2-hexyl group Alkyl groups such as branched alkyl groups such as 3-hexyl group; cyclopropyl group, cyclobutyl group, A group in which part or all of the hydrogen atoms of an alicyclic hydrocarbon group such as a cyclopentyl group, norbornyl group, adamantyl group and the like are substituted with a halogen atom), a hydroxyalkyl group (for example, a hydroxymethyl group, etc.), etc. It is done.

Regarding the alkyl group, alicyclic hydrocarbon group, and aryl group represented by R ⁵ , the description of each group represented by R ³ and R ⁴ can be applied. In addition, as said alkyl group, a C1-C6 alkyl group is preferable and a methyl group, an ethyl group, and n-propyl group are more preferable. Examples of the aralkyl group represented by R ⁵ include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group.

In the group represented by —M (R ⁶ ) ₃ of R ⁵ , the description of the alkyl group represented by R ³ and R ⁴ can be applied as the alkyl group represented by R ⁶ .

The cyclic ether structure which may be formed by bonding R ³ and R ⁵ to each other is preferably a cyclic ether structure having 3 to 20 ring members, more preferably a cyclic ether structure having 5 to 8 ring members, and tetrahydrofuran. And tetrahydropyran are more preferred.

  Examples of the group represented by the above formula (2) include a group represented by the following formula.

  Examples of the monomer that gives the structural unit (I) include 1-ethoxyethyl methacrylate, 1-methoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 1-isobutoxyethyl methacrylate, 1-methacrylic acid 1- t-butoxyethyl, 1- (2-chloroethoxy) ethyl methacrylate, 1- (2-ethylhexyloxy) ethyl methacrylate, 1-n-propoxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, 1-methacrylic acid 1- (2-Cyclohexylethoxy) ethyl, 1-benzyloxyethyl methacrylate, 2-tetrahydropyranyl methacrylate, 1-ethoxyethyl acrylate, 1-methoxyethyl acrylate, 1-n-butoxyethyl acrylate, acrylic acid 1 -Isobutoxyethyl, acrylic 1-t-butoxyethyl, 1- (2-chloroethoxy) ethyl acrylate, 1- (2-ethylhexyloxy) ethyl acrylate, 1-n-propoxyethyl acrylate, 1-cyclohexyloxyethyl acrylate, acrylic acid 1- (2-cyclohexylethoxy) ethyl, 1-benzyloxyethyl acrylate, 2-tetrahydropyranyl acrylate, 5,6-di (1- (trimethylsilanyloxy) ethoxy) carbonyl) -2-norbornene, 5 , 6-Di (1- (trimethylgermyloxy) ethoxy) carbonyl) -2-norbornene, 5,6-di (1-methoxyethoxycarbonyl) -2-norbornene, 5,6-di (1- (cyclohexyloxy) ) Ethoxycarbonyl) -2-norbornene, 5,6-di (1- (benzylo) Ii) ethoxycarbonyl) -2-norbornene, p or m-1-ethoxyethoxystyrene, p or m-1-methoxyethoxystyrene, p or m-1-n-butoxyethoxystyrene, p or m-1-isobutoxy Ethoxystyrene, p or m-1- (1,1-dimethylethoxy) ethoxystyrene, p or m-1- (2-chloroethoxy) ethoxystyrene, p or m-1- (2-ethylhexyloxy) ethoxystyrene, p or m-1-n-propoxyethoxystyrene, p or m-1-cyclohexyloxyethoxystyrene, p or m-1- (2-cyclohexylethoxy) ethoxystyrene, p or m-1-benzyloxyethoxystyrene, etc. Can be mentioned.

  Among these, the monomer that gives the structural unit (I) is preferably a structural unit containing an acid-dissociable group represented by the above formula (2), such as 1-ethoxyethyl methacrylate, 1-n-butoxy methacrylate. Ethyl, 2-tetrahydropyranyl methacrylate, 1-benzyloxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate are more preferable, and 2-tetrahydropyranyl methacrylate is more preferable.

  [A] The content of the structural unit (I) in the polymer is not particularly limited as long as the effect of the present invention is achieved, but [A] the monomer preparation with respect to all the structural units contained in the polymer The ratio is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and further preferably 15 to 65% by mass.

[Structural unit (II)]
The structural unit (II) is a structural unit containing a polymerizable group. [A] When the polymer has the structural unit (II), the interlayer insulating film for a display element formed from the positive radiation-sensitive composition has more excellent surface hardness, heat resistance, solvent resistance and voltage. Can have retention.

  The structural unit (II) is not particularly limited as long as it is a structural unit containing a polymerizable group, but the epoxy group-containing structural unit (II-1) and the (meth) acryloyl group-containing structural unit (II-2) are preferred structures. Listed as a unit. Below, an epoxy group containing structural unit and a (meth) acryloyl group containing structural unit are explained in full detail.

[Epoxy group-containing structural unit (II-1)]
The epoxy group-containing structural unit (II-1) is not particularly limited as long as it is a structural unit having an epoxy group in the structural unit. Examples of the epoxy group-containing monomer that gives such a structural unit (II-1) include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 3-methyl-3,4 acrylate. -Epoxybutyl, 3-ethyl-3,4-epoxybutyl methacrylate, 5,6-epoxyhexyl (meth) acrylate, 5-methyl-5,6-epoxyhexyl methacrylate, 5-ethyl-5-methacrylate 6-epoxyhexyl, 6,7-epoxyheptyl (meth) acrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclo (meth) acrylate Hexylethyl, 3,4-epoxycyclohexylpropyl methacrylate, 3,4-epoxycyclomethacrylate Xylbutyl, 3,4-epoxycyclohexylhexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylethyl acrylate, 3,4-epoxycyclohexylpropyl acrylate Oxiranyl group-containing (meth) acrylic compounds such as 3,4-epoxycyclohexylbutyl acrylate, 3,4-epoxycyclohexylhexyl acrylate;
o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, α-methyl-o-vinylbenzylglycidyl ether, α-methyl-m-vinylbenzylglycidyl ether, α-methyl-p-vinyl Vinyl benzyl glycidyl ethers such as benzyl glycidyl ether;
vinyl phenyl glycidyl ethers such as o-vinyl phenyl glycidyl ether, m-vinyl phenyl glycidyl ether, p-vinyl phenyl glycidyl ether;
3-acryloyloxymethyloxetane, 3-acryloyloxymethyl-3-methyloxetane, 3-acryloyloxymethyl-3-ethyloxetane, 3-acryloyloxymethyl-3-phenyloxetane, 3- (2-acryloyloxyethyl) oxetane 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -3-phenyloxetane, 3-methacryloyloxy Methyl oxetane, 3-methacryloyloxymethyl-3-methyloxetane, 3-methacryloyloxymethyl-3-ethyloxetane, 3-methacryloyloxymethyl-3-phenyloxetane, 3- (2-methacryloyloxye) Oxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-phenyloxetane, 2 -Acryloyloxymethyloxetane, 2-acryloyloxymethyl-2-methyloxetane, 2-acryloyloxymethyl-2-ethyloxetane, 2-acryloyloxymethyl-2-phenyloxetane, 2- (2-acryloyloxyethyl) oxetane, 2- (2-acryloyloxyethyl) -2-ethyloxetane, 2- (2-acryloyloxyethyl) -2-ethyloxetane, 2- (2-acryloyloxyethyl) -2-phenyloxetane, 2-methacryloyloxymethyl Oh Cetane, 2-methacryloyloxymethyl-2-methyloxetane, 2-methacryloyloxymethyl-2-ethyloxetane, 2-methacryloyloxymethyl-2-phenyloxetane, 2- (2-methacryloyloxyethyl) oxetane, 2- (2 -Methacryloyloxyethyl) -2-ethyloxetane, 2- (2-methacryloyloxyethyl) -2-ethyloxetane, 2- (2-methacryloyloxyethyl) -2-phenyloxetane, and other oxetanyl group-containing (meth) acrylic compounds Compounds and the like.

  Among the above epoxy group-containing monomers, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-methacryloyloxymethyl-3-methyloxetane 3-methacryloyloxymethyl-3-ethyloxetane is preferable from the viewpoint of copolymerization reactivity with other monomers and developability of the positive radiation sensitive composition. These monomers can be used alone or in combination of two or more.

[(Meth) acryloyl group-containing structural unit (II-2)]
The (meth) acryloyl group-containing structural unit (II-2) is not particularly limited as long as it is a structural unit having a (meth) acryloyloxy group as a polymerizable group.

  [A] As a method for introducing the structural unit (II-2) into a polymer, for example, a polymer of a monomer containing an unsaturated compound having at least one hydroxyl group in one molecule (hereinafter referred to as “[A1] And a method of reacting an unsaturated isocyanate compound.

  [A1] Monomers used for polymer synthesis include (meth) acrylic acid hydroxyalkyl ester, (meth) acrylic acid dihydroxyalkyl ester, (meth) acrylic acid (6-hydroxyhexanoyloxy) alkyl ester, and the like. Is mentioned.

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

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

  The [A1] polymer obtained as described above may be used for the synthesis of the [A] polymer as it is in the polymerization reaction solution. After the [A1] polymer is once separated from the solution, the [A] polymer is You may use for the synthesis | combination of coalescence.

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

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

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

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

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

  [A] As another method for introducing the structural unit (II-1) into the polymer, for example, a monomer polymer containing an unsaturated compound having at least one carboxyl group in one molecule (hereinafter referred to as “[ A2 ”polymer”) and a compound having a vinyl ether group and a (meth) acryloyloxy group are reacted.

  [A2] The method for synthesizing the polymer includes, for example, a method of polymerizing a carboxyl group-containing monomer from the viewpoint of easy material acquisition and synthesis.

  [A2] Examples of monomers used for polymer synthesis include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic acid monoester, itaconic acid monoester, and the like. It is done. Of these, (meth) acrylic acid is preferred.

  Examples of the compound having a vinyl ether group and a (meth) acryloyloxy group include a compound represented by the following formula (3).

In the formula (3), ^{R 7} is a hydrogen atom or a methyl group. R ⁸ is a divalent linking group. R ⁹ is a hydrogen atom or a monovalent organic group.

Examples of the divalent linking group represented by R ⁸ include a linear, branched or cyclic alkylene group having 2 to 18 carbon atoms, an alkoxyalkylene group having 2 to 20 carbon atoms, and 2 to 8 carbon atoms. A halogenated alkylene group, a polyethylene glycol skeleton excluding a terminal hydroxyl group, a polypropylene glycol skeleton excluding a terminal hydroxyl group, a polybutylene glycol skeleton excluding a terminal hydroxyl group, and an aryl group. Examples of the monovalent organic group represented by R ⁹ include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms and an optionally substituted aromatic group having 6 to 11 carbon atoms. Is mentioned.

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

  Of these compounds having a vinyl ether group and a (meth) acryloyloxy group, a compound represented by the above formula (3) is preferable, and 2- (vinyloxyethoxy) ethyl (meth) acrylate is more preferable. As commercially available products of 2- (vinyloxyethoxy) ethyl (meth) acrylate, for example, VEEA as 2- (vinyloxyethoxy) ethyl acrylate, VEEM as 2- (vinyloxyethoxy) ethyl methacrylate ( As mentioned above, the product made from Nippon Shokubai etc. is mentioned.

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

  [A] As another method for introducing the structural unit (II-2) into the polymer, for example, using a polyfunctional (meth) acrylate as a monomer, together with a monomer that gives the structural unit (I), etc. Examples include a method of copolymerization.

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

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

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

  The structural unit (II) preferably has two or more (meth) acryloyloxy groups. When the structural unit (II) has two or more (meth) acryloyloxy groups, it is possible to realize better sensitivity and to form an interlayer insulating film for a display element having excellent surface hardness, heat resistance, and the like.

  [A] The content of the structural unit (II) in the polymer is not particularly limited as long as the desired effect of the invention of the present application is exhibited, and [A] a single amount with respect to all the structural units contained in the polymer. The body charge ratio is preferably 5% by mass to 60% by mass, more preferably 7% by mass to 55% by mass, and particularly preferably 10% by mass to 50% by mass.

[Structural unit (III)]
The structural unit (III) is a structural unit represented by the above formula (1). [A] The polymer has a structural unit (III), and when R ² in the above formula (1) is an alkyl group, alkenyl group, alkynyl group or acyloxyalkyl group having 6 to 30 carbon atoms, a polymer The rigidity of the main chain skeleton can be reduced to lower the glass transition point, and when R ² is a bridged cyclic hydrocarbon group, entanglement between molecular chains can be reduced. As described above, the high flexibility before curing of the [A] polymer allows the positive radiation-sensitive composition to promote the diffusion of the acid generated during exposure and further improve the sensitivity. it can.

In said formula (1), R < ¹ > is a hydrogen atom or a methyl group. R ² is an alkyl group having 6 to 30 carbon atoms, an alkenyl group, an alkynyl group, or an acyloxyalkyl group, or a bridged cyclic hydrocarbon group having 4 to 30 carbon atoms. However, a part of hydrogen atoms of the alkyl group, alkenyl group, alkynyl group, acyloxyalkyl group and bridged cyclic hydrocarbon group may be substituted with a hydroxyl group or a carboxyl group.

The group represented by R ² is not an acid dissociable group, and the structural unit (III) is a structural unit other than the structural unit (I).

Examples of the alkyl group having 6 to 30 carbon atoms represented by R ² include a linear or branched alkyl group having 6 to 30 carbon atoms, specifically, a hexyl group, a heptyl group, and an octyl group. Group, nonyl group, decyl group, undecyl group, dodecyl group, hexadecyl group, stearyl group, hebenyl group and the like. Among these, an alkyl group having 6 to 20 carbon atoms is preferable, an alkyl group having 10 to 20 carbon atoms is more preferable, and a dodecyl group, a hexadecyl group, and a stearyl group are further preferable.

Examples of the alkenyl group having 6 to 30 carbon atoms represented by R ² include a hexenyl group, a heptenyl group, an octenyl group, a decenyl group, an undecenyl group, a dodecenyl group, and a hexadecenyl group.

Examples of the alkynyl group having 6 to 30 carbon atoms represented by R ² include a hexynyl group, a heptynyl group, an octynyl group, a decynyl group, an undecynyl group, a dodecynyl group, and a hexadecynyl group.

Examples of the acyloxyalkyl group having 6 to 30 carbon atoms represented by R ² include lauryloxyethyl group, lauryloxypropyl group, stearoyloxyethyl group, stearoyloxypropyl group, and oleoyloxyethyl group. And oleoyloxypropyl group. Furthermore, the group etc. which the glycidyl group modified | denatured with oleic acid or soybean fat fatty acid were mentioned.

Examples of the bridged cyclic hydrocarbon group having 4 to 30 carbon atoms represented by R ² include a norcaranyl group (bicyclo [5.1.0] heptyl group) and a norpinanyl group (bicyclo [3.1.0]). Heptyl group), norbornyl group (bicyclo [2.2.1] heptyl group), adamantyl group, bicyclo [2.2.2] octyl group, bicyclo [3.2.1] octyl group, tricyclo [2.2. 1.0 ^2,6 ] heptyl group, tricyclo [5.2.1.0 ^2,6 ] decanyl group, tricyclo [5.3.1.1 ^2,6 ] dodecyl group, tricyclo [4.4.1. 1 ^1,5 ] dodecyl group, caranyl group, pinanyl group, bornyl group and the like. Among these, a bridged cyclic hydrocarbon group having 6 to 20 carbon atoms is preferable, and an adamantyl group and a tricyclo [5.2.1.0 ^2,6 ] decanyl group are more preferable.

Examples of the bridged cyclic hydrocarbon group having 4 to 30 carbon atoms represented by R ² include a group obtained by condensing rings including the rings exemplified above. Examples of the group in which the rings are condensed include a group having a shape in which a bridged ring such as a norbornane ring and a single ring such as a cycloheptane ring or a cyclohexane ring or a polycyclic ring such as a decahydronaphthalene ring are condensed, Group having a shape in which is condensed, and examples of such a group include a group represented by the following formula.

Examples of the monomer that gives the structural unit (III) include hexyl (meth) acrylate,
(Meth) acrylate heptyl, (meth) acrylate octyl, (meth) acrylate nonyl, (meth) acrylate decyl, (meth) acrylate undecyl, (meth) acrylate dodecyl, methacrylate hexadecyl, stearyl methacrylate, A monomer containing an alkyl group having 6 to 30 carbon atoms or an acyloxyalkyl group, such as a compound in which hebenyl methacrylate or glycidyl methacrylate is modified with oleic acid or soybean oil fatty acid;
Norcaranyl (meth) acrylate, norpinanyl (meth) acrylate, norbornyl (meth) acrylate, adamantyl (meth) acrylate, bicyclo [2.2.2] octyl (meth) acrylate, bicyclo (meth) acrylate [ 3.2.1] Octyl, (meth) acrylic acid tricyclo [2.2.1.0 ^2,6 ] heptyl, (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decanyl, (meta ) Tricyclo [5.3.1.1 ^2,6 ] dodecyl acrylate, tricyclo [4.4.1.1 ^1,5 ] dodecyl (meth) acrylate, caranyl (meth) acrylate, (meth) acrylic acid And monomers containing a bridged cyclic hydrocarbon group having 4 to 30 carbon atoms such as pinanyl and bornyl (meth) acrylate. Of these, dodecyl methacrylate, adamantyl methacrylate and stearyl methacrylate are preferred.

  [A] The content of the structural unit (III) in the polymer is preferably 3 mol% or more and 50 mol% or less, more preferably 5 mol% or more and 50 mol% or less, further preferably 10 mol% or more and 25 mol% or less. preferable. By making the content rate of structural unit (III) into the said range, the said positive radiation sensitive composition can accelerate | stimulate the spreading | diffusion of an acid more, and can improve a sensitivity more.

[Other structural units]
[A] The polymer may have other structural units in addition to the structural unit (I), the structural unit (II) and the structural unit (III) as long as the effects of the present invention are not impaired. Examples of the monomer that gives other structural units include a monomer having a carboxyl group or a derivative thereof, a monomer having a hydroxyl group, and other monomers. In addition, these other structural units do not include the structural units included in the structural units (I) to (III).

  Examples of the monomer having a carboxyl group or a derivative thereof include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, Examples thereof include monocarboxylic acids such as 2-methacryloyloxyethyl hexahydrophthalic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and acid anhydrides of the above dicarboxylic acids.

  Examples of the monomer having a hydroxyl group include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxymethylcyclohexylmethyl acrylate; methacrylic acid 2 -Hydroxyethyl, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl methacrylate, 4-hydroxymethyl methacrylate-hydroxyalkyl methacrylate and the like. It is done. Of these monomers having a hydroxyl group, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and methacrylic acid 2 are used from the viewpoint of heat resistance of the obtained interlayer insulating film for display elements. -Hydroxyethyl, 4-hydroxybutyl methacrylate, 4-hydroxymethyl-cyclohexylmethyl acrylate, 4-hydroxymethyl-cyclohexylmethyl methacrylate are preferred.

Examples of other monomers include alkyl acrylates such as methyl acrylate and i-propyl acrylate;
Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate;
Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] acrylate Decyl-8-yloxy) ethyl, cycloaliphatic alkyl acrylates such as isobornyl acrylate;
Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] methacrylate) Decane-8-yloxy) ethyl, cycloaliphatic alkyl methacrylates such as isobornyl methacrylate;
Aryl esters of acrylic acid such as phenyl acrylate and benzyl acrylate or aralkyl of acrylic acid;
Aryl esters of methacrylic acid such as phenyl methacrylate and benzyl methacrylate or aralkyl of methacrylic acid;
Dialkyl dicarboxylates such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Unsaturated hetero 5-membered methacrylic acid ester or unsaturated hetero 6-membered methacrylic acid containing 1 atom of oxygen such as tetrahydrofurfuryl methacrylate, tetrahydrofuryl methacrylate, tetrahydropyran-2-methyl methacrylate;
4-methacryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-cyclohexyl- 2 oxygen atoms such as 1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane An unsaturated heterocyclic 5-membered methacrylic acid containing:
4-acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-acryloyloxymethyl-2, 2-diethyl- 1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-acryloyloxymethyl-2-cyclopentyl-1,3-dioxolane, 4-acryloyloxymethyl-2- Cyclohexyl-1,3-dioxolane, 4-acryloyloxyethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-acryloyloxypropyl-2-methyl-2-ethyl-1,3-dioxolane, 4- Acryloyloxybutyl-2-methyl-2-ethyl-1,3-dioxola Unsaturated five-membered heterocyclic acrylic acid containing oxygen 2 atoms and the like;
Vinyl aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, 4-isopropenylphenol;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -N-substituted maleimides such as maleimide propionate, N- (9-acridinyl) maleimide;
Conjugated diene compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene;
And unsaturated compounds such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride and vinyl acetate.

Among these other monomers, styrene, 4-isopropenylphenol, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, tetrahydrofurfuryl methacrylate, 1,3-butadiene 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, N-cyclohexylmaleimide, N-phenylmaleimide, benzyl methacrylate is a monomer having the above carboxyl group or a derivative thereof, a hydroxyl group From the viewpoints of copolymerization reactivity with a monomer having a photodegradability and developability of the positive radiation sensitive composition.

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

[A] The number average molecular weight (Mn) in terms of polystyrene by GPC of the polymer is preferably 2.0 × 10 ^{3 to} 1.0 × 10 ⁵ , more preferably 5.0 × 10 ^{3 to} 5.0 × 10. ⁴ . [A] By making Mn of a polymer into the said specific range, the cure reactivity at the time of hardening of the coating film of the said positive type radiation sensitive composition can be improved.

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

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

<[A] Polymer Synthesis Method>
[A] The polymer can be produced, for example, by polymerizing a monomer corresponding to each predetermined structural unit in a suitable solvent using a radical polymerization initiator. For example, a method of dropping a solution containing a monomer and a radical initiator into a reaction solvent or a solution containing the monomer to cause a polymerization reaction, a solution containing the monomer, and a solution containing the radical initiator Separately, a method of dropping a reaction solvent or a monomer-containing solution into a polymerization reaction, a plurality of types of solutions containing each monomer, and a solution containing a radical initiator, It is preferable to synthesize by a method such as a method of dropping it into a reaction solvent or a solution containing a monomer to cause a polymerization reaction.

  [A] Examples of the solvent used in the polymerization reaction of the polymer include the solvents exemplified in the section of the preparation of the positive radiation-sensitive composition described later.

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

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

<[B] Radiation sensitive acid generator>
[B] The radiation-sensitive acid generator is a compound that generates an acid upon irradiation with radiation. As the radiation, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used. When the positive radiation sensitive composition contains [B] a radiation sensitive acid generator, the positive radiation sensitive composition can exhibit positive radiation sensitive characteristics.

  [B] Examples of the radiation-sensitive acid generator include oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylic acid ester compounds. In addition, each of these [B] radiation sensitive acid generators can be used individually or in combination of 2 or more types.

[Oxime sulfonate compound]
Examples of the oxime sulfonate compound include a compound containing an oxime sulfonate group represented by the following formula (4).

In the formula (4), R ¹⁰ is a linear or branched alkyl group, alicyclic hydrocarbon group or an aryl group. However, in these groups, some or all of the hydrogen atoms may be substituted.

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

  Examples of the compound containing an oxime sulfonate group represented by the above formula (4) include an oxime sulfonate compound represented by the following formula (5).

In said formula (5), R < ¹⁰ > is synonymous with said formula (4). X is an alkyl group, an alkoxy group, or a halogen atom. r is an integer of 0-3. However, when there are a plurality of Xs, the plurality of Xs may be the same or different.

  The alkyl group that can be represented by X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group represented by X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom represented by X is preferably a chlorine atom or a fluorine atom. r is preferably 0 or 1. In the above formula (5), a compound in which r is 1, X is a methyl group, and the substitution position of X is ortho is preferable.

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

  Compound (5-1) (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, Compound (5-2) (5-octylsulfonyloxyimino-5H-thiophene- 2-Ilidene)-(2-methylphenyl) acetonitrile, Compound (5-3) (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, Compound (5-4) (5 -P-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile and compound (5-5) (5-octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile are commercially available. Available as a product.

[Onium salt]
Examples of the onium salt include diphenyliodonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, and tetrahydrothiophenium salt.

  Examples of the diphenyliodonium salt include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyliodonium. Butyltris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoroarsenate Bis (4-t-butylphenyl) iodonium trifluorome Sulphonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium-p-toluenesulfonate, bis (4-t-butylphenyl) iodonium camphorsulfonic acid, etc. .

  Examples of the triphenylsulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, triphenylsulfonium. And butyl tris (2,6-difluorophenyl) borate.

  Examples of the sulfonium salt include alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts, substituted benzylsulfonium salts and the like.

  Examples of the alkylsulfonium salt include 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (Benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate and the like can be mentioned.

  Examples of the benzylsulfonium salt include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenyl. Methylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenyl Examples include methylsulfonium hexafluorophosphate.

  Examples of the dibenzylsulfonium salt include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyl dibenzylsulfonium hexafluoroantimonate, and dibenzyl-4-methoxyphenylsulfonium. Hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl- Examples include 4-hydroxyphenylsulfonium hexafluorophosphate.

  Examples of substituted benzylsulfonium salts include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and p-chlorobenzyl-4-hydroxyphenylmethyl. Sulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3- Examples include chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate.

  Examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, and 3- (p-methoxybenzyl). ) Benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, and the like.

  Examples of tetrahydrothiophenium salts include 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate and 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethane. Sulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-1,1 , 2,2-Tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (5-t-butoxycarbonyloxybicyclo) [2.2.1] Heptan-2-yl) -1,1, , 2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (6-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl ) -1,1,2,2-tetrafluoroethanesulfonate and the like.

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

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

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

[Sulfone compound]
Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds, diaryldisulfone compounds, and the like.

[Sulfonic acid ester compounds]
Examples of the sulfonate compound include alkyl sulfonate, haloalkyl sulfonate, aryl sulfonate, and imino sulfonate.

[Carboxylic ester compounds]
Examples of the carboxylic acid ester compound include carboxylic acid o-nitrobenzyl ester.

  [B] The radiation-sensitive acid generator is preferably an oxime sulfonate compound, an onium salt, or a sulfonate compound from the viewpoints of sensitivity and solubility. As the oxime sulfonate compound, a compound represented by the above formula (4) is preferable, a compound represented by the above formula (5) is more preferable, and is represented by the above formula (5-1), which is available as a commercial product. Are particularly preferred. As the onium salt, tetrahydrothiophenium salt and benzylsulfonium salt are preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate and benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate are preferable. More preferred. As the sulfonic acid ester compound, a haloalkylsulfonic acid ester is preferable, and N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester is more preferable.

  The content of the [B] radiation sensitive acid generator in the positive radiation sensitive composition is preferably 0.1 parts by mass to 10 parts by mass, more preferably 100 parts by mass of the [A] polymer. Is 1 part by mass to 5 parts by mass. [B] By setting the content of the radiation-sensitive acid generator within the above specified range, the sensitivity of the positive radiation-sensitive composition is optimized, and the interlayer insulation for display elements having high surface hardness while maintaining transparency A film can be formed.

<[C] Compound>
The compound [C] is a compound having a molecular weight of 1,000 or less and containing one or more (meth) acryloyl groups. The positive radiation-sensitive composition can have higher sensitivity by containing the [C] compound, and the surface hardness, heat resistance, and the like of a cured film such as an interlayer insulating film for a display element to be formed. Solvent resistance, voltage holding ratio, etc. can be improved.

  [C] The compound is not particularly limited as long as it is a compound containing at least one (meth) acryloyl group in the molecule. Examples of the compound having one (meth) acryloyl group include acrylamide, (meth) acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, and isobornyloxyethyl. (Meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (Meth) acrylate, lauryl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopenteni (Meth) acrylate, N, N-dimethyl (meth) acrylamide tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2- Tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, vinylcaprolactam, N-vinylpyrrolidone, phenoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, pentachlorophenyl Meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, bornyl (meth) acrylate, and methyl triethylene diglycol (meth) acrylate. Of these compounds having one (meth) acryloyl group, isobornyl (meth) acrylate, lauryl (meth) acrylate, and phenoxyethyl (meth) acrylate are preferred. As these commercial products, for example, Aronix M-101, M-102, M-111, M-113, M-117, M-152, TO-1210 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TC-110S, R -564, R-128H (above, Nippon Kayaku), biscoat 192, biscoat 220, biscoat 2311HP, biscoat 2000, biscoat 2100, biscoat 2150, biscoat 8F, biscoat 17F (above, manufactured by Osaka Organic Chemical Industry), etc. .

  Examples of the compound containing two or more (meth) acryloyl groups include ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, and tricyclodecane. Diyldimethylene di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (Meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide (hereinafter referred to as “EO”) modified trimethylolpropane tri (meth) acrylate, propylene Xoxide (hereinafter referred to as “PO”) modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bisphenol A diglycidyl ether at both ends (meth) acrylic acid Adduct, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, Polyethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate Caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di (meth) acrylate EO-modified hydrogenated bisphenol A di (meth) acrylate, PO-modified hydrogenated bisphenol A di (meth) acrylate, EO-modified bisphenol F di (meth) acrylate, (meth) acrylate of phenol novolac polyglycidyl ether, and the like. Examples of commercially available compounds containing two or more of these (meth) acryloyl groups include SA1002 (manufactured by Mitsubishi Chemical), biscoat 195, biscoat 230, biscoat 260, biscoat 215, biscoat 310, biscoat 214HP, biscoat 295, and biscoat 300. Biscoat 360, biscoat GPT, biscoat 400, biscoat 700, biscoat 540, biscoat 3000, biscoat 3700 (above, manufactured by Osaka Organic Chemical Industry), Kayarad R-526, HDDA, NPGDA, TPGDA, MANDA, R-551, R- 712, R-604, R-684, PET-30, GPO-303, TMPTA, THE-330, DPHA, DPHA-2H, DPHA-2C, DPHA-2I, D-310, D-330, D CA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, T-1420, T-2020, T-2040, TPA-320, TPA-330, RP-1040, RP- 2040, R-011, R-300, R-205 (Nippon Kayaku Co., Ltd.), Aronix M-210, M-220, M-233, M-240, M-215, M-305, M-309 M-310, M-315, M-325, M-400, M-6200, M-6400 (above, manufactured by Toagosei Co., Ltd.), light acrylate BP-4EA, BP-4PA, BP-2EA, BP-2PA, DCP-A (above, manufactured by Kyoeisha Chemical Co., Ltd.), New Frontier BPE-4, BR-42M, GX-8345 (above, manufactured by Daiichi Kogyo Seiyaku), ASF-400 (Nippon Chemical Co., Ltd.) ), Lipoxy SP-1506, SP-1507, SP-1509, VR-77, SP-4010, SP-4060 (above, Showa Polymer), NK ester A-BPE-4 (above, Shin-Nakamura Chemical Co., Ltd.) Manufactured) and the like.

  Of these, compounds containing at least two (meth) acryloyl groups in the molecule are preferred, and compounds containing at least three (meth) acryloyl groups in the molecule are more preferred. Examples of the compound containing at least three (meth) acryloyl groups in the molecule include the tri (meth) acrylate compounds, tetra (meth) acrylate compounds, penta (meth) acrylate compounds, and hexa (meth) exemplified above. It can be selected from acrylate compounds and the like.

  Among these, as the [C] compound, a skeleton derived from a diol structure having 2 to 12 carbon atoms represented by the following formula (6), a skeleton derived from trimethylolpropane represented by the formula (7), a formula (8) And a compound having a pentaerythritol-derived skeleton represented by formula (9) or a dipentaerythritol-derived skeleton represented by formula (9).

  In said formula (6), n is an integer of 2-12.

  As such a preferable [C] compound, for example, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, Examples include ditrimethylolpropane tetra (meth) acrylate, ethylene oxide-modified dipentaerythritol hexaacrylate, propylene oxide-modified dipentaerythritol hexaacrylate, ε-caprolactan-modified dipentaerythritol hexaacrylate, and succinic acid-modified pentaerythritol triacrylate. In addition, in the said positive type radiation sensitive composition, a [C] compound can be used individually by 1 type or in combination of 2 or more types. The [C] compound is a compound having a molecular weight of 1,000 or less.

  The content of the [C] compound in the positive radiation-sensitive composition is preferably 1% by mass or more and 50% by mass or less, more preferably 1% by mass or more and 30% by mass or less in terms of solid content. Preferably, it is 1 mass% or more and 20 mass% or less. By setting the content of the [C] compound in the positive radiation sensitive composition in the above range, the surface hardness, solvent resistance, heat resistance and voltage holding of a cured film such as an interlayer insulating film for display elements to be formed are maintained. The rate can be further improved.

<Other optional components>
In addition to the [A] polymer, the [B] radiation sensitive acid generator and the [C] compound, the positive radiation sensitive composition includes a sensitizer and a basic compound as long as the effects of the present invention are not impaired. You may contain other arbitrary components, such as a compound, surfactant, close_contact | adherence adjuvant, and the compound which has a hindered phenol structure. In addition, each component may be used individually by 1 type, and may use 2 or more types together. Hereinafter, each component will be described in detail.

[Sensitizer]
The positive radiation sensitive composition preferably further contains a sensitizer as a suitable component. When the positive radiation sensitive composition further contains a sensitizer, the sensitivity of the positive radiation sensitive composition can be further improved. The sensitizer absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer in an electronically excited state is brought into contact with the photoacid generator, causing effects such as electron transfer, energy transfer, and heat generation. As a result, the radiation sensitive acid generator [B] undergoes a chemical change. Decomposes to produce acid.

  Examples of the sensitizer include compounds belonging to the following compounds and having an absorption wavelength in the region of 350 nm to 450 nm.

Examples of the sensitizer include polynuclear fragrances such as pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, and 9,10-dipropyloxyanthracene. Tribe;
Xanthenes such as fluorescein, eosin, erythrosine, rhodamine B, rose bengal;
Xanthones such as xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone, isopropylthioxanthone;
Cyanines such as thiacarbocyanine, oxacarbocyanine;
Merocyanines such as merocyanine and carbomerocyanine;
Rhodocyanines;
Oxonols;
Thiazines such as thionine, methylene blue and toluidine blue;
Acridines such as acridine orange, chloroflavin, acriflavine;
Acridones such as acridone, 10-butyl-2-chloroacridone;
Anthraquinones such as anthraquinone;
Squariums such as squalium;
Styryls;
Base styryls such as 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole;
7-diethylamino 4-methylcoumarin, 7-hydroxy 4-methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H [l] benzopyrano [6.7.8-ij] quinolidine- Coumarins, such as 11-non, etc. are mentioned.

  Of these [C] sensitizers, polycyclic aromatics, xanthones, acridones, styryls, base styryls and coumarins are preferred, polycyclic aromatics and xanthones are more preferred, and 9,10- Dibutoxyanthracene and isopropylthioxanthone are particularly preferred.

  As content of the sensitizer in the said positive radiation sensitive composition, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] polymers, and 0.5 mass part-5 mass parts. Is more preferable. Sensitivity can be improved more by making content of a sensitizer into the said range.

[Basic compounds]
The basic compound can be arbitrarily selected from those used in chemically amplified resists, and examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and carboxylic acid quaternary ammonium salts. Can be mentioned. By including a basic compound in the positive radiation-sensitive composition, the diffusion length of the acid generated from the [B] radiation-sensitive acid generator by exposure can be appropriately controlled, and the pattern developability is improved. it can.

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

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

  Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4 -Dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, pyrazole , Pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.3.0] -7 undecene Etc.

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

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

  Of these 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 basic compound in the said positive radiation sensitive composition, 0.001 mass part-1 mass part are preferable with respect to 100 mass parts of [A] polymers, and 0.005 mass part-0.2. Part by mass is more preferable. Pattern developability improves more by making content of a basic compound into the said specific range.

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

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

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

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

  The content of the surfactant in the positive radiation-sensitive composition is preferably 0.01 parts by mass or more and 2 parts by mass or less, more preferably 0.8 parts by mass with respect to 100 parts by mass of the [A] polymer. It is 05 parts by mass or more and 1 part by mass or less. The film thickness uniformity of a coating film can be improved more by making content of surfactant into the said specific range.

[Adhesion aid]
The adhesion aid can be used to improve the adhesion between an insulating material and an inorganic substance serving as a substrate, for example, a silicone compound such as silicone, silicone oxide, or silicon nitride, or a metal such as gold, copper, or aluminum. As the adhesion assistant, a functional silane coupling agent is preferable. Examples of the functional silane coupling agent include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group (preferably an oxiranyl group), and a thiol group.

  Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltri Examples include methoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. Of these, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane are preferred. .

  The content of the adhesion assistant in the positive radiation sensitive composition is preferably 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polymer [A], and is 1 part by mass or more and 10 parts by mass. The following is more preferable. By setting the content of the adhesion aid in the specific range, the adhesion between the formed display element interlayer insulating film and the substrate is further improved.

[Compound having a hindered phenol structure]
A compound having a hindered phenol structure is a component for preventing cleavage of a compound bond by a radical or a peroxide. Examples of the compound having a hindered phenol structure include radical scavengers such as a compound having a hindered amine structure in addition to a compound having a hindered phenol structure.

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

  Examples of the compound having a hindered amine structure include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 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, , 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) decandioate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl Oxy] -1- [2- (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy) ethyl] -2,2,6,6-tetramethylpiperidine, 2-methyl-2 -(2,2,6,6-tetramethyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6- Tetramethyl-4 Compounds such as piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate It is done.

  As content of the compound which has a hindered phenol structure in the said positive radiation sensitive composition, 0.1 mass part or more and 10 mass parts or less are preferable with respect to 100 mass parts of [A] polymers, 1.5. More preferred is 3 parts by mass or more. By setting the content of the compound having a hindered phenol structure within the above specified range, the voltage holding ratio of the interlayer insulating film for a display element to be formed is further improved while maintaining the sensitivity of the positive radiation sensitive composition. be able to.

<Preparation method of positive radiation sensitive composition>
The positive radiation-sensitive composition is dissolved or dispersed by mixing [A] polymer, [B] radiation-sensitive acid generator, [C] compound, and other optional components as required in a solvent. Prepared. For example, the positive radiation-sensitive composition can be prepared by mixing each component at a predetermined ratio in a solvent.

  As the solvent, a solvent in which each component is uniformly dissolved or dispersed and does not react with each component is preferably used. Examples of the solvent include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, and aromatic hydrocarbons. , Ketones, other esters and the like.

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

  Examples of ethers include tetrahydrofuran.

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

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

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

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

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

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

  Examples of aromatic hydrocarbons include toluene and xylene.

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

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

  Of these solvents, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and butyl methoxyacetate are preferred. Diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, propylene More preferred are glycol monomethyl ether and butyl methoxyacetate.

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

The method for forming an interlayer insulating film for a display element according to the present invention includes:
(1) Using the positive radiation sensitive composition, a step of forming a coating film on a substrate (hereinafter also referred to as “step (1)”),
(2) A step of irradiating at least a part of the coating film (hereinafter also referred to as “step (2)”),
(3) a step of developing the coating film irradiated with the radiation (hereinafter also referred to as “step (3)”), and (4) a step of heating the developed coating film (hereinafter referred to as “step (4)”). Is also called)
Have

  According to the formation method, an interlayer insulating film for a display element that is excellent in surface hardness, solvent resistance, heat resistance, and voltage holding ratio can be formed. Moreover, the interlayer insulation film for display elements which has a fine and elaborate pattern can be easily formed by using the said positive type radiation sensitive composition excellent in a sensitivity. Therefore, the formed interlayer insulation film for display elements can be used suitably for display elements, such as a liquid crystal display element and an organic EL display element.

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

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

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

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

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

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

  The film thickness of the formed interlayer insulation film for display elements is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, and particularly preferably 0.1 μm to 4 μm.

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

<[A] Synthesis of polymer>
[Synthesis Example 1]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 50 parts by mass of tetrahydropyranyl methacrylate giving structural unit (I), 35 parts by mass of glycidyl methacrylate giving structural unit (II), 5 parts by mass of dodecyl methacrylate giving structural unit (III), and other structural units After 10 parts by weight of methacrylic acid and 3 parts by weight of α-methylstyrene dimer were charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-1). Mw of the copolymer (A-1) was 9,000. Moreover, the solid content concentration of the polymer solution obtained here was 32.1 mass%.

[Synthesis Example 2]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 50 parts by mass of tetrahydropyranyl methacrylate giving structural unit (I), 20 parts by mass of glycidyl methacrylate giving structural unit (II), 20 parts by mass of dodecyl methacrylate giving structural unit (III), and other structural units After 10 parts by weight of methacrylic acid and 3 parts by weight of α-methylstyrene dimer were charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-2). Mw of the copolymer (A-2) was 8,000. Moreover, the solid content concentration of the polymer solution obtained here was 31.5 mass%.

[Synthesis Example 3]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 50 parts by mass of tetrahydropyranyl methacrylate giving structural unit (I), 20 parts by mass of glycidyl methacrylate giving structural unit (II), 20 parts by mass of adamantyl methacrylate giving structural unit (III), and other structural units After 10 parts by weight of methacrylic acid and 3 parts by weight of α-methylstyrene dimer were charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-3). Mw of the copolymer (A-3) was 8,500. Moreover, the solid content concentration of the polymer solution obtained here was 32.5 mass%.

[Synthesis Example 4]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 50 parts by mass of tetrahydropyranyl methacrylate giving structural unit (I), 20 parts by mass of glycidyl methacrylate giving structural unit (II), 20 parts by mass of stearyl methacrylate giving structural unit (III), and other structural units After 10 parts by weight of methacrylic acid and 3 parts by weight of α-methylstyrene dimer were charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-4). Mw of the copolymer (A-4) was 7,500. Moreover, the solid content concentration of the polymer solution obtained here was 31.0 mass%.

[Synthesis Example 5]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 15 parts by mass of tetrahydropyranyl methacrylate giving structural unit (I), 10 parts by mass of glycidyl methacrylate giving structural unit (II), 60 parts by mass of dodecyl methacrylate giving structural unit (III), and other structural units After 5 parts by weight of methacrylic acid to be fed and 3 parts by weight of α-methylstyrene dimer were charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-5). Mw of the copolymer (A-5) was 8,000. Moreover, the solid content concentration of the polymer solution obtained here was 31.5 mass%.

[Synthesis Example 6]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 55 parts by mass of tetrahydropyranyl methacrylate giving structural unit (I), 35 parts by mass of glycidyl methacrylate giving structural unit (II), and 10 parts by mass of methacrylic acid giving other structural units and 3 parts by mass of α-methylstyrene dimer After the part was charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (a-1). Mw of the copolymer (a-1) was 9,000. Moreover, the solid content concentration of the polymer solution obtained here was 32.1 mass%.

<Preparation of positive radiation sensitive composition>
[Example 1]
[A] As a polymer, in a solution containing the copolymer (A-1) (an amount corresponding to 100 parts by mass (solid content) of the copolymer (A-1)), [B] a radiation-sensitive acid generator. 3 parts by mass of the compound (B-1), 15 parts by mass of the compound (C-1) as the [C] compound, 0.01 parts by mass of the compound (D-1) as the basic compound, and (E -1) 0.2 parts by mass of a silicone-based surfactant (Toray Dow Corning, SH 8400 FLUID), and (F-1) 3.0 parts by mass of γ-glycidoxypropyltrimethoxysilane as an adhesion assistant The positive radiation sensitive composition (S-1) was prepared by mixing and filtering with a membrane filter having a pore diameter of 0.2 μm.

[Examples 2 to 10 and Comparative Example 1]
The positive radiation sensitive compositions (S-2) to (S-10) and (CS-) were operated in the same manner as in Example 1 except that the types and amounts of the components were as shown in Table 1. 1) were prepared, and were designated as Examples 2 to 10 and Comparative Example 1, respectively.

Hereinafter, the components used for the preparation of the positive radiation sensitive compositions of Examples and Comparative Examples will be described in detail.
<[B] Radiation sensitive acid generator>
(B-1): 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate (B-2): N-hydroxynaphthalimide-trifluoromethanesulfonate (B-3): ( 5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (manufactured by Ciba Specialty Chemicals, IRGACURE PAG 103)

<[C] Compound>
(C-1) a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (C-2) ethylene oxide-modified dipentaerythritol hexaacrylate,
(C-3) trimethylolpropane triacrylate (C-4) succinic acid modified pentaerythritol triacrylate (C-5) ε-caprolactan modified dipentaerythritol hexaacrylate (C-6) hexamethylene diacrylate

<Basic compound>
(D-1) 4-Dimethylaminopyridine

<Surfactant>
(E-1) Silicone surfactant (Toray Dow Corning, SH 8400 FLUID)

<Adhesion aid>
(F-1) γ-Glycidoxypropyltrimethoxysilane

<Evaluation>
The positive radiation sensitive compositions of Examples 1 to 10 and Comparative Example 1 were used, and various properties as each positive radiation sensitive composition and its coating film or interlayer insulating film were evaluated as follows. The results are shown in Table 1.

[Sensitivity (J / m ² )]
Hexamethyldisilazane (HMDS) was applied onto a 550 × 650 mm chromium film and heated at 60 ° C. for 1 minute (HMDS treatment). Each positive radiation-sensitive composition prepared as described above is applied onto the chromium film-formed glass after the HMDS treatment using a slit die coater “TR6321055-CL”, and the ultimate pressure is set to 100 Pa and vacuum is applied. After removing the solvent below, the coating film was further baked at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. Then, after using a Canon MPA-600FA exposure machine and irradiating the coating film with a variable exposure amount through a mask having a 60 μm line and space (10 to 1) pattern, 0 Developed with a 4 mass% tetramethylammonium hydroxide aqueous solution at 25 ° C. by a puddle method. The development time was 80 seconds. Next, washing with running ultrapure water for 1 minute was performed, followed by drying to form a pattern on the chromium-deposited glass substrate after the HMDS treatment. At this time, the amount of exposure necessary to completely dissolve the 6 μm space pattern was examined. It can be said that the sensitivity is good when this value is 300 J / m ² or less.

[surface hardness]
Similar to the sensitivity evaluation, a coating film was formed on a glass substrate. This glass without exposure
The substrate was heated at 220 ° C. for 1 hour in a clean oven to obtain a cured film. The pencil hardness (surface hardness) of the cured film was measured by the 8.4.1 pencil scratch test of JIS K-5400-1990. When this value is 3H or larger, the surface hardness as a cured film such as an interlayer insulating film is good, and it can be said that the composition used for forming the cured film has sufficient curability.

[Solvent resistance (%)]
Similar to the sensitivity evaluation, a coating film was formed on a glass substrate. Without exposure, this glass substrate was heated at 220 ° C. for 1 hour in a clean oven to obtain a cured film. About the board | substrate which has this cured film, the film thickness (T1) of the obtained cured film was measured with the laser microscope (VK-8510, product made from Keyence). Next, the glass substrate on which the cured film was formed was immersed in dimethyl sulfoxide whose temperature was controlled at 70 ° C. for 20 minutes, and then the thickness (t1) of the cured film was measured. The rate of change in thickness (%) was determined and defined as solvent resistance (%).
Solvent resistance (%) = {(t1-T1) / T1} × 100
When the absolute value of this value was less than 5%, the solvent resistance was judged to be excellent.

[Voltage holding ratio]
Each positive-type positive-type radiation-sensitive composition is spun on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions is formed on the surface, and an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape. After coating, pre-baking was performed for 10 minutes in a clean oven at 90 ° C. to form a coating film having a thickness of 2.0 μm. Next, the coating film was exposed at an exposure amount of 500 J / m ² without using a photomask. Thereafter, the coating film was cured by post-baking at 230 ° C. for 30 minutes. Next, the substrate on which the pixels are formed and the substrate on which the ITO electrode is simply deposited in a predetermined shape are bonded together with a sealing agent mixed with 0.8 mm glass beads, and then Merck liquid crystal MLC6608 is injected into the liquid crystal. A cell was produced. Further, the liquid crystal cell was placed in a constant temperature layer at 60 ° C., and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage holding ratio measuring system (VHR-1A type, Toyo Technica Co., Ltd.). The applied voltage at this time is a square wave of 5.5 V, and the measurement frequency is 60 Hz. The voltage holding ratio (%) is a value obtained from the following formula.
Voltage holding ratio (%) = (potential difference of liquid crystal cell after 16.7 milliseconds / voltage applied at 0 milliseconds) × 100
If the voltage holding ratio of the liquid crystal cell is 90% or less, it means that the liquid crystal cell cannot hold the applied voltage at a predetermined level for a time of 16.7 milliseconds, and the liquid crystal cannot be sufficiently aligned. There is a high risk of causing "burn-in".

[Heat-resistant]
Similar to the sensitivity evaluation, a coating film was formed on a glass substrate. Without exposure, this glass substrate was heated at 220 ° C. for 1 hour in a clean oven to obtain a cured film. The cured film thus obtained was measured for a 5% thermogravimetric decrease temperature. TGA was used for the measurement, and the temperature was raised from room temperature to 500 ° C. at 10 ° C./min under air, and the temperature at which the mass decreased by 5% was measured. It can be judged that the higher the temperature at which the mass is reduced by 5%, the better the heat resistance.

  As is clear from the results in Table 1, Examples 1 to 10 using the positive radiation sensitive composition have better sensitivity than the composition of Comparative Example 1, and have surface hardness and solvent resistance. It was also found that a cured film having excellent heat resistance can be formed. In addition, the cured films formed from the positive radiation sensitive compositions of Examples 1 to 10 also had a sufficiently high voltage holding ratio.

  Since the positive radiation sensitive composition of the present invention is excellent in sensitivity, an interlayer insulating film for a display element having a fine and elaborate pattern can be easily formed. In addition, the positive radiation sensitive composition can form an interlayer insulating film for a display element that is excellent in surface hardness, solvent resistance, heat resistance, and voltage holding ratio. Therefore, the positive radiation sensitive composition is suitable as a material for forming an interlayer insulating film for display elements such as liquid crystal display elements and organic EL display elements.

Claims (8)

[A] a polymer having a structural unit (I) containing an acid dissociable group, a structural unit (II) containing a polymerizable group, and a structural unit (III) represented by the following formula (1);
[B] a radiation sensitive acid generator, and
[C] a compound having a molecular weight of 1,000 or less containing one or more (meth) acryloyl groups ,
[C] The positive radiation sensitive composition whose content of a compound is 1 mass% or more and 50 mass% or less in conversion of solid content .

(In Formula (1), R ¹ is a hydrogen atom or a methyl group. R ² is an alkyl group having 6 to 30 carbon atoms, an alkenyl group, an alkynyl group, an acyloxyalkyl group, or a bridge having 4 to 30 carbon atoms. A cyclic cyclic hydrocarbon group, provided that a part of the hydrogen atoms of the alkyl group, alkenyl group, alkynyl group, acyloxyalkyl and bridged cyclic hydrocarbon group is substituted with a hydroxyl group or a carboxyl group. May be.) The positive radiation sensitive composition according to claim 1, wherein the acid dissociable group in the structural unit (I) is represented by the following formula (2).

(In Formula (2), R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group or an aryl group, provided that these alkyl groups and alicyclic hydrocarbon groups are Alternatively, some or all of the hydrogen atoms of the aryl group may be substituted, and R ³ and R ⁴ are not both hydrogen atoms, and R ⁵ is an alkyl group or an alicyclic hydrocarbon group. , An aralkyl group, an aryl group, or a group represented by —M (R ⁶ ) _3. M is Si, Ge, or Sn, R ⁶ is an alkyl group, provided that an alkyl group of R ⁵ , Some or all of the hydrogen atoms of the alicyclic hydrocarbon group, the aralkyl group, the aryl group, and the alkyl group of R ⁶ may be substituted, and R ³ and R ⁵ are bonded to each other, and R ³ is oxygen atoms carbon atoms and R ⁵ bonded to that is bonded Together may form a cyclic ether structure.) The positive radiation sensitive composition according to claim 1 or 2, wherein the polymerizable group in the structural unit (II) is an epoxy group. [A] The positive radiation sensitive composition according to claim 1 , wherein the content of the structural unit (III) in the polymer is 3% by mass or more and 50% by mass or less. [C] compounds, derived structure diol structure having 2 to 12 carbon atoms, derived from trimethylol propane skeleton, claim 1 is a compound having a skeleton or dipentaerythritol derived skeleton from pentaerythritol of claim 4 The positive radiation-sensitive composition according to any one of the above. The positive radiation-sensitive composition according to any one of claims 1 to 5 , which is used for forming an interlayer insulating film for a display element. The interlayer insulation film for display elements formed with the positive radiation sensitive composition of Claim 6 . (1) A step of forming a coating film on a substrate using the positive radiation sensitive composition according to claim 6 ;
(2) A step of irradiating at least a part of the coating film with radiation,
(3) A process for developing the coating film irradiated with the radiation, and (4) a process for heating the developed coating film.