JP5488176B2 - Positive radiation-sensitive composition, interlayer insulating film and method for forming the same - Google Patents

Description

  The present invention relates to a positive radiation sensitive composition suitable as a material for forming an interlayer insulating film of a display element such as a liquid crystal display element (LCD) or an organic EL display element (OLED), and an interlayer insulating film formed from the composition. And a method of forming the interlayer insulating film.

  The display element is generally provided with an interlayer insulating film for the purpose of insulating between wirings arranged in layers. As the material for forming the interlayer insulating film, positive radiation-sensitive compositions are widely used because the number of steps for obtaining a necessary pattern shape is small and a material having sufficient flatness is preferable. The positive radiation sensitive composition used in forming such an interlayer insulating film is required to have good radiation sensitivity and storage stability, and the obtained interlayer insulating film is required to have excellent heat resistance and transparency. .

  As a component of the positive radiation sensitive composition, an acrylic resin is widely adopted. For example, JP 2009-98673 A has a structural unit containing an acid dissociable group, and this acid dissociation property. Resin that becomes alkali-soluble when the group is dissociated, Resin having a structural unit containing a functional group that can react with a carboxyl group to form a covalent bond (such as an epoxy group), and a positive photosensitive material containing an acid generator Compositions have been proposed. This composition is a mixture of the above two types of specific resins, and contains a carboxyl group generated from a resin having a structural unit containing an acid dissociable group by the action of an acid after the formation of a coating film, an epoxy group, and the like. It is configured to be cured by a crosslinking reaction with a resin having a structural unit. However, the surface hardness and solvent resistance of the obtained cured film are not satisfactory levels due to insufficient progress of the crosslinking reaction.

JP 2009-98673 A

  In order to cope with such a current situation, it is conceivable to promote a crosslinking reaction by adding an amine compound used as a curing agent for an epoxy material. However, the addition of a general amine compound may cause a reaction with time with an epoxy group present in the composition, resulting in a decrease in storage stability.

  Therefore, it is also conceivable to protect the amine compound with a protecting group capable of leaving with an acid to reduce the reactivity to ensure the storage stability of the composition. In addition, if the protecting group is eliminated by an acid generated in the process of forming the cured film, the amine compound can be subjected to a crosslinking reaction with an epoxy group. However, in this case, the reaction in which the alkali-insoluble resin becomes alkali-soluble due to the dissociation of the acid-dissociable group and the crosslinking reaction with the amine compound of the epoxy group proceed simultaneously, and the composition exhibits positive radiation sensitive characteristics. There is a risk that it can no longer be demonstrated.

  The present invention has been made based on the above circumstances, and its purpose is to provide an interlayer insulating film having excellent surface hardness and solvent resistance, and having transmittance and voltage holding ratio which are general required characteristics. A positive-type radiation-sensitive composition that can be formed and has excellent storage stability and sufficient radiation sensitivity, an interlayer insulating film formed from the composition, and a method for forming the interlayer insulating film is there.

（式（Ｉ）中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、アルキル基、シクロアルキル又はアリール基であり、これらのアルキル基、シクロアルキル基又はアリール基の水素原子の一部又は全部が置換基で置換されていてもよい（但し、Ｒ^１及びＲ^２が共に水素原子である場合はない）。Ｒ^３は、アルキル基、シクロアルキル基、アラルキル基、アリール基又は−Ｍ（Ｒ^３ｍ）_３で表される基（ＭはＳｉ、Ｇｅ又はＳｎであり、Ｒ^３ｍはアルキル基である。）であり、これらの水素原子の一部又は全部が置換基で置換されていてもよい。Ｒ^１とＲ^３とが連結して環状エーテルを形成してもよい。）

（式（ＩＩ）中、Ｒ^４は、炭素数１〜４のアルキル基又は炭素数４〜２０の１価の脂環式炭化水素基である。Ｒ^５及びＲ^６は、それぞれ独立して、炭素数１〜４のアルキル基若しくは炭素数４〜２０の１価の脂環式炭化水素基であるか、又はＲ^５及びＲ^６が互いに結合して、それらが結合している炭素原子と共に炭素数４〜２０の２価の脂環式炭化水素基を形成する。＊は窒素原子と結合する結合手である。） The invention made to solve the above problems is
[A] In the same or different polymer molecules, a structural unit (1) containing a group represented by the following formula (I), an epoxy group-containing structural unit, and a structure represented by the following formula (II) A polymer (hereinafter also referred to as “[A] polymer”) having a structural unit (2) containing a bonded group (hereinafter also referred to as “nitrogen-containing group”), and [B] an acid generator It is a positive radiation sensitive composition.

(In Formula (I), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and a part of the hydrogen atoms of these alkyl group, cycloalkyl group or aryl group) Alternatively, all may be substituted with a substituent (provided that R ¹ and R ² are not both hydrogen atoms) R ³ represents an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, or —M (R ^3m ) is a group represented by ₃ (M is Si, Ge or Sn, R ^3m is an alkyl group), and some or all of these hydrogen atoms are substituted with substituents. R ¹ and R ³ may be linked to form a cyclic ether.)

(In the formula (II), R ⁴ is an alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms. R ⁵ and R ⁶ are each independently An alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or R ⁵ and R ⁶ are bonded to each other, and carbon together with the carbon atom to which they are bonded (Forms a divalent alicyclic hydrocarbon group of formula 4 to 20. * is a bond bonded to a nitrogen atom.)

  The positive radiation sensitive composition employs the [A] polymer introduced with the structural unit (2), and the structural unit (2) introduces a protecting group into the nitrogen atom portion as an amine structure. Containing nitrogen-containing groups with carbamate structure. Thereby, the said positive radiation sensitive composition can suppress the reactivity of a nitrogen-containing structure at the time of storage, and can improve storage stability. Further, by adopting a specific carbamate structure as the protection form of the nitrogen-containing group, it is possible to deprotect from the activation energy for dissociation by the acid of the structure represented by the above formula (II) as the acid dissociable group The activation energy is increased. As a result, the nitrogen-containing group is not deprotected by the acid generated from the [B] acid generator at the time of exposure, and the [B] acid generator is generated by heat during post-baking after development and its heat. It will be deprotected by the cooperative action with the acid generated from. Therefore, the positive radiation-sensitive composition can exhibit positive radiation-sensitive characteristics in a series of steps from exposure to development, and crosslinks an epoxy group with a nitrogen-containing group that is deprotected during post-baking. The reaction can proceed sufficiently and an interlayer insulating film having excellent surface hardness and solvent resistance can be formed.

（式（２−１）中、Ｒ^４、Ｒ^５及びＲ^６の定義は上記式（ＩＩ）と同じである。Ｒ^７は水素原子又はメチル基であり、Ｘは炭素数１〜２０の２価の炭化水素基である。Ｒ^８は水素原子又は炭素数１〜２０の１価の炭化水素基であり、Ｘ及びＲ^８が互いに結合して、それらが結合している窒素原子と共に炭素数４〜２０の複素環構造を形成してもよい。） In the positive radiation sensitive composition, the structural unit (2) is a structural unit represented by the following formula (2-1) (hereinafter also referred to as “structural unit (2-1)”). preferable.

(In Formula (2-1), the definitions of R ⁴ , R ⁵ and R ⁶ are the same as those in Formula (II) above. R ⁷ is a hydrogen atom or a methyl group, and X is 2 having 1 to 20 carbon atoms. R ⁸ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and X and R ⁸ are bonded to each other, together with the nitrogen atom to which they are bonded, 4 to 20 heterocyclic structures may be formed.)

  When the structural unit (2) specifically has a specific structure represented by the formula (2-1), the monomer that gives the structural unit (2) has excellent polymerizability. The incorporation ratio of the unit (2) into the [A] polymer can be increased, whereby the positive radiation-sensitive composition can exhibit an excellent epoxy group crosslinking function. As a result, an interlayer insulating film obtained using the positive radiation sensitive composition can exhibit excellent surface hardness and solvent resistance.

  The positive radiation sensitive composition can be suitably used for forming an interlayer insulating film of a display element.

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

  By the formation method of the present invention using the positive radiation sensitive composition, an interlayer insulating film having excellent surface hardness and solvent resistance, and sufficient transmittance and voltage holding ratio can be formed.

  An interlayer insulating film of a display element formed from the positive radiation sensitive composition is also suitably included in the present invention.

  As described above, the positive radiation-sensitive composition of the present invention contains the above-described components [A] and [B], thereby satisfying the general required characteristics of transmittance and voltage holding ratio in a well-balanced manner. In addition, an interlayer insulating film having excellent surface hardness and solvent resistance can be formed. Moreover, the positive radiation sensitive composition has excellent storage stability and exhibits sufficient radiation sensitivity.

  The positive radiation sensitive composition of the present invention contains a [A] polymer and a [B] acid generator, and may further contain other optional components.

<[A] polymer>
[A] The polymer has the structural unit (1), the epoxy group-containing structural unit, and the structural unit (2) in the same or different polymer molecules, and other structural units as necessary. It may be. The embodiment of the [A] polymer having the structural unit (1), the epoxy group-containing structural unit and the structural unit (2) is not particularly limited. For example, (i) the structural unit (1) in one polymer molecule, When all of the epoxy group-containing structural unit and the structural unit (2) are present, and [A] one polymer molecule is present in the polymer,
(Ii) having a structural unit (1) and an epoxy group-containing structural unit in one polymer molecule, and having a structural unit (2) in a different polymer molecule, [A] in the polymer If there are two polymer molecules in
(Iii) One polymer molecule has the structural unit (1) and the structural unit (2), and a polymer molecule different from the structural unit (1) has an epoxy group-containing structural unit, and [A] If there are two polymer molecules in
(Iv) It has an epoxy group-containing structural unit and a structural unit (2) in one polymer molecule, and has a structural unit (1) in a different polymer molecule, [A] in the polymer If there are two polymer molecules in
(V) having a structural unit (1) in one polymer molecule, and having an epoxy group-containing structural unit in a polymer molecule different from the structural unit (1), and further having a structural unit (2 And [A] when three kinds of polymer molecules are present in the polymer,
(Vi) When each of the polymer molecules specified in (i) to (v) is included in combination (vii) In addition to the polymer molecules specified in (i) to (vi), [A] is further separated in the polymer In the case where one or two or more polymer molecules are present. In either case, the effects of the present invention can be enjoyed. Hereinafter, the structural unit (1), the epoxy group-containing structural unit, the structural unit (2), and other structural units will be described in order.

<Structural unit (1)>
In the structural unit (1), the group represented by the above formula (I) is present as a group that dissociates in the presence of an acid to generate a polar group (hereinafter also simply referred to as “acid-dissociable group”). Therefore, the acid-dissociable group is dissociated by the acid generated from the acid generator upon irradiation with radiation, and as a result, the [A] polymer that has been insoluble in alkali becomes alkali-soluble. The acid dissociable group has an acetal structure or a ketal structure that is relatively stable with respect to an alkali, and these are dissociated by the action of an acid.

Examples of the alkyl group represented by R ¹ and R ² in the above formula (I) include linear and branched alkyl groups having 1 to 30 carbon atoms, and an oxygen atom and a sulfur atom in the alkyl chain. And may have a nitrogen atom. Specific examples of the alkyl group include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, and n-tetradecyl group. A branched alkyl group such as a straight-chain alkyl group such as n-octadecyl group, i-propyl group, i-butyl group, t-butyl group, neopentyl group, 2-hexyl group, 3-hexyl group Can do.

In the above formula (I), the cycloalkyl group represented by R ¹ and R ² is preferably a cycloalkyl group having 3 to 20 carbon atoms, may be polycyclic, and has an oxygen atom in the ring. Also good. Specific examples of the cycloalkyl group 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.

In the above formula (I), the aryl group represented by R ¹ and R ² is preferably an aryl group having 6 to 14 carbon atoms, which may be a single ring or a structure in which single rings are connected, It may be a condensed ring. Specific examples of the aryl group include a phenyl group and a naphthyl group.

Some or all of the hydrogen atoms of R ¹ and R ² may be substituted with a substituent. As such a substituent, for example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (for this cycloalkyl group, the description of the cycloalkyl group can be preferably applied. ), An aryl group (as the aryl group, the above description of the aryl group can be preferably applied), an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, such as a methoxy group, ethoxy Group, propoxy group, n-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, etc.), acyl group (preferably an acyl group having 2 to 20 carbon atoms, for example, acetyl Group, propionyl group, butyryl group, i-butyryl group, etc.), acyloxy group (preferably An acyloxy group having 2 to 10 carbon atoms, such as an acetoxy group, an ethylyloxy group, a butyryloxy group, a t-butyryloxy group, a t-amylyloxy group, etc.), an alkoxycarbonyl group (preferably having a carbon number of 2 to 20). An alkoxycarbonyl group, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, etc.), a haloalkyl group (a part or all of the hydrogen atoms of the alkyl group or cycloalkyl group are substituted with halogen atoms). And examples thereof include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a fluorocyclopropyl group, and a fluorocyclobutyl group. As for the cyclic structure in the aryl group, cycloalkyl group and the like, examples of the further substituent include the above alkyl groups.

In the above formula (I), the description of R ¹ and R ² can be applied to the alkyl group, cycloalkyl group and aryl group represented by R ³ . The aralkyl group represented by R ³ in the above formula (I) is preferably an aralkyl group having 7 to 20 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group. . The group represented by ^{-M (R} _{3m) 3} of ^{R 3} in the above formula (1), for example trimethylsilanyl group, trimethylgermyl group and the like. As the substituent which may substitute part or all of the hydrogen atoms of the aralkyl group represented by R ³ or the group represented by —M (R ^3m ) ₃ , the above substituents are preferably employed. be able to.

R ¹ and R ³ may be linked to form a cyclic ether. Examples of such cyclic ethers include 2-oxetanyl group, 2-tetrahydrofuranyl group, 2-tetrahydropyranyl group, 2-dioxanyl group and the like. Some or all of the hydrogen atoms of the cyclic ether may be substituted with the above substituents.

  The structural unit (1) can have an acetal structure or a ketal structure by having a functional group that should have an acetal structure or a ketal structure by bonding to another carbon atom.

  Examples of the functional group that should have an acetal structure by bonding to the other carbon atom include 1-methoxyethoxy group, 1-ethoxyethoxy group, 1-n-propoxyethoxy group, 1-i-propoxyethoxy. Group, 1-n-butoxyethoxy group, 1-i-butoxyethoxy group, 1-sec-butoxyethoxy group, 1-t-butoxyethoxy group, 1-cyclopentyloxyethoxy group, 1-cyclohexyloxyethoxy group, 1- Norbornyloxyethoxy group, 1-bornyloxyethoxy group, 1-phenyloxyethoxy group, 1- (1-naphthyloxy) ethoxy group, 1-benzyloxyethoxy group, 1-phenethyloxyethoxy group, (cyclohexyl) (Methoxy) methoxy group, (cyclohexyl) (ethoxy) methoxy group (Cyclohexyl) (n-propoxy) methoxy group, (cyclohexyl) (i-propoxy) methoxy group, (cyclohexyl) (cyclohexyloxy) methoxy group, (cyclohexyl) (phenoxy) methoxy group, (cyclohexyl) (benzyloxy) methoxy group , (Phenyl) (methoxy) methoxy group, (phenyl) (ethoxy) methoxy group, (phenyl) (n-propoxy) methoxy group, (phenyl) (i-propoxy) methoxy group, (phenyl) (cyclohexyloxy) methoxy group , (Phenyl) (phenoxy) methoxy group, (phenyl) (benzyloxy) methoxy group, (benzyl) (methoxy) methoxy group, (benzyl) (ethoxy) methoxy group, (benzyl) (n-propoxy) methoxy group, Benzyl) (i-propo Ii) methoxy group, (benzyl) (cyclohexyloxy) methoxy group, (benzyl) (phenoxy) methoxy group, (benzyl) (benzyloxy) methoxy group, 2-tetrahydrofuranyloxy group, 2-tetrahydropyranyloxy group, 1 -A trimethylsilanyloxyethoxy group, a 1-trimethylgermyloxyethoxy group, etc. can be mentioned.

  Among these, 1-ethoxyethoxy group, 1-cyclohexyloxyethoxy group, 2-tetrahydropyranyloxy group, 1-n-propoxyethoxy group, and 2-tetrahydropyranyloxy group can be mentioned as preferable examples.

  Examples of the functional group that should have a ketal structure by bonding to the other carbon atom include 1-methyl-1-methoxyethoxy group, 1-methyl-1-ethoxyethoxy group, 1-methyl- 1-n-propoxyethoxy group, 1-methyl-1-i-propoxyethoxy group, 1-methyl-1-n-butoxyethoxy group, 1-methyl-1-i-butoxyethoxy group, 1-methyl-1- sec-butoxyethoxy group, 1-methyl-1-t-butoxyethoxy group, 1-methyl-1-cyclopentyloxyethoxy group, 1-methyl-1-cyclohexyloxyethoxy group, 1-methyl-1-norbornyloxy Ethoxy group, 1-methyl-1-bornyloxyethoxy group, 1-methyl-1-phenyloxyethoxy group, 1-methyl-1- (1-na Tiloxy) ethoxy group, 1-methyl-1-benzyloxyoxyethoxy group, 1-methyl-1-phenethyloxyethoxy group, 1-cyclohexyl-1-methoxyethoxy group, 1-cyclohexyl-1-ethoxyethoxy group, 1- Cyclohexyl-1-n-propoxyethoxy group, 1-cyclohexyl-1-i-propoxyethoxy group, 1-cyclohexyl-1-cyclohexyloxyethoxy group, 1-cyclohexyl-1-phenoxyethoxy group, 1-cyclohexyl-1-benzyl Oxyethoxy group, 1-phenyl-1-methoxyethoxy group, 1-phenyl-1-ethoxyethoxy group, 1-phenyl-1-n-propoxyethoxy group, 1-phenyl-1-i-propoxyethoxy group, Phenyl-1-cyclohexyloxyethoxy group 1-phenyl-1-phenyloxyethoxy group, 1-phenyl-1-benzyloxyethoxy group, 1-benzyl-1-methoxyethoxy group, 1-benzyl-1-ethoxyethoxy group, 1-benzyl-1-n- Propoxyethoxy group, 1-benzyl-1-i-propoxyethoxy group, 1-benzyl-1-cyclohexyloxyethoxy group, 1-benzyl-1-phenyloxyethoxy group, 1-benzyl-1-benzyloxyethoxy group, 2 -(2-Methyl-tetrahydrofuranyl) oxy group, 2- (2-methyl-tetrahydropyranyl) oxy group, 1-methoxy-cyclopentyloxy group, 1-methoxy-cyclohexyloxy group and the like can be mentioned.

  Among these, 1-methyl-1-methoxyethoxy group and 1-methyl-1-cyclohexyloxyethoxy group can be mentioned as preferable ones.

  Specific examples of the structural unit (1) having the acetal structure or ketal structure include structural units represented by the following formulas (1-1) to (1-3).

（式（１−１）及び（１−３）中、Ｒ´は水素原子又はメチル基である。Ｒ^１、Ｒ^２及びＲ^３は上記式（Ｉ）の説明と同義である。）

(In the formulas (1-1) and (1-3), R ′ is a hydrogen atom or a methyl group. R ¹ , R ² and R ³ have the same meanings as in the description of the above formula (I).)

As a monomer having radical polymerizability that gives the structural unit (1) represented by the above formulas (1-1) to (1-3) (hereinafter also simply referred to as “acetal structure-containing monomer”). For example, 1-alkoxyalkyl (meth) acrylate, 1- (cycloalkyloxy) alkyl (meth) acrylate, 1- (haloalkoxy) alkyl (meth) acrylate, 1- (aralkyloxy) alkyl (meth) acrylate, tetrahydropyrani (Meth) acrylate-based acetal structure-containing monomers such as ru (meth) acrylate;
2,3-di (1- (trialkylsilanyloxy) alkoxy) carbonyl) -5-norbornene, 2,3-di (1- (trialkylgermyloxy) alkoxy) carbonyl) -5-norbornene, 2, 3-di (1-alkoxyalkoxycarbonyl) -5-norbornene, 2,3-di (1- (cycloalkyloxy) alkoxycarbonyl) -5-norbornene, 2,3-di (1- (aralkyloxy) alkoxycarbonyl ) Norbornene-based acetal structure-containing monomers such as -5-norbornene;
Examples thereof include styrene acetal structure-containing monomers such as 1-alkoxyalkoxystyrene, 1- (haloalkoxy) alkoxystyrene, 1- (aralkyloxy) alkoxystyrene, and tetrahydropyranyloxystyrene.

  Among these, 1-alkoxyalkyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, 1-alkoxyalkoxystyrene, and tetrahydropyranyloxystyrene are preferable, and 1-alkoxyalkyl (meth) acrylate is more preferable.

Specific examples of the acetal structure-containing monomer that gives the structural unit (1) include, for example,
1-ethoxyethyl methacrylate, 1-methoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 1-isobutoxyethyl methacrylate, 1-t-butoxyethyl methacrylate, 1- (2-chloroethoxy) ethyl methacrylate, 1- (2 -Ethylhexyloxy) methacrylates such as 1-n-propoxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, 1- (2-cyclohexylethoxy) ethyl methacrylate, 1-benzyloxyethyl methacrylate, 2-tetrahydropyranyl methacrylate Acetal structure-containing monomer;
1-ethoxyethyl acrylate, 1-methoxyethyl acrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl acrylate, 1-t-butoxyethyl acrylate, 1- (2-chloroethoxy) ethyl acrylate, 1- (2 -Ethylhexyloxy) ethyl acrylate, 1-n-propoxyethyl acrylate, 1-cyclohexyloxyethyl acrylate, 1- (2-cyclohexylethoxy) ethyl acrylate, 1-benzyloxyethyl acrylate, 2-tetrahydropyranyl acrylate, etc. Acetal structure-containing monomer;
2,3-di (1- (trimethylsilanyloxy) ethoxy) carbonyl) -5-norbornene, 2,3-di (1- (trimethylgermyloxy) ethoxy) carbonyl) -5-norbornene, 2,3- Di (1-methoxyethoxycarbonyl) -5-norbornene, 2,3-di (1- (cyclohexyloxy) ethoxycarbonyl) -5-norbornene, 2,3-di (1- (benzyloxy) ethoxycarbonyl) -5 A monomer containing a norbornene-based acetal structure such as norbornene;
p or m-1-ethoxyethoxystyrene, p or m-1-methoxyethoxystyrene, p or m-1-n-butoxyethoxystyrene, p or m-1-isobutoxyethoxystyrene, p or m-1- ( 1,1-dimethylethoxy) ethoxystyrene, p or m-1- (2-chloroethoxy) ethoxystyrene, p or m-1- (2-ethylhexyloxy) ethoxystyrene, p or m-1-n-propoxyethoxy Styrene acetal structure-containing monomers such as styrene, p or m-1-cyclohexyloxyethoxystyrene, p or m-1- (2-cyclohexylethoxy) ethoxystyrene, p or m-1-benzyloxyethoxystyrene, etc. Can be mentioned. The said structural unit (1) can be used 1 type or in combination of 2 or more types.

  Among the acetal structure-containing monomers that give the structural unit (1), 1-ethoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 2-tetrahydropyranyl methacrylate, and 1-benzyloxyethyl methacrylate are preferable.

  A commercially available thing may be used for the acetal structure containing monomer which gives structural unit (1), and what was synthesize | combined by the well-known method can also be used. For example, the acetal structure-containing monomer that gives the structural unit (1) represented by the above formula (1-1) reacts (meth) acrylic acid with vinyl ether in the presence of an acid catalyst as shown below. Can be synthesized.

（式中、Ｒ´、Ｒ^１及びＲ^３は、それぞれ上記式（１−１）におけるＲ´、Ｒ^１及びＲ^３に対応し、Ｒ^２１及びＲ^２２は、−ＣＨ（Ｒ^２１）（Ｒ^２２）として、上記式（１−１）におけるＲ^２に対応する。）

(In the formula, R ′, R ¹ and R ³ respectively correspond to R ′, R ¹ and R ³ in the above formula (1-1), and R ²¹ and R ²² represent —CH (R ²¹ ) (R ²² ) corresponds to R ² in the above formula (1-1).)

  [A] The content of the structural unit (1) in the polymer is not particularly limited as long as the polymer [A] is alkali-soluble by acid and exhibits the desired heat resistance of the cured film. When the polymer molecule has the structural unit (1), the epoxy group-containing structural unit, and the structural unit (2), the monomer charge ratio is 5% by mass with respect to all structural units contained in the [A] polymer. 70 mass% or less is preferable, 10 mass% or more and 60 mass% or less are more preferable, and 20 mass% or more and 50 mass% or less are especially preferable.

  On the other hand, among the essential three structural units, when one polymer molecule has the structural unit (1) alone or the structural unit (1) and the epoxy group-containing structural unit or structural unit (2), the structural unit (1 The content of the structural unit (1) in the one polymer molecule having) is 5% by mass or more and 60% by mass or less in the monomer charge ratio with respect to all the structural units contained in the polymer molecule. Is preferably 10% by mass or more and 50% by mass or less, and particularly preferably 15% by mass or more and 45% by mass or less.

<Epoxy group-containing structural unit>
[A] A polymer has an epoxy group containing structural unit with the said structural unit (1) and the below-mentioned structural unit (2). The epoxy group-containing structural unit is a structural unit derived from an epoxy group-containing monomer having radical polymerizability. Examples of the epoxy group include an oxiranyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure). [A] When the polymer has a structural unit containing an oxiranyl group or an oxetanyl group in the molecule, the surface hardness and solvent resistance of the cured film obtained from the positive radiation-sensitive composition can be further increased. .

Specific examples of the epoxy group-containing monomer that gives the epoxy group-containing structural unit include, for example, glycidyl acrylate, glycidyl methacrylate, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, and acrylic. Acid-3-methyl-3,4-epoxybutyl, methacrylate-3-ethyl-3,4-epoxybutyl, acrylic acid-5,6-epoxyhexyl, methacrylic acid-5,6-epoxyhexyl, methacrylic acid Contains epoxyalkyl groups such as 5-methyl-5,6-epoxyhexyl, methacrylic acid-5-ethyl-5,6-epoxyhexyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl (Meth) acrylic compounds;
3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylethyl methacrylate, 3,4-epoxycyclohexylpropyl methacrylate, 3,4-epoxycyclohex Xylbutyl methacrylate, 3,4-epoxycyclohexylhexyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylethyl acrylate, 3,4 -Epoxy cycloalkyl group-containing (meth) acrylic compounds such as epoxy cyclohexyl propyl acrylate, 3,4-epoxy cyclohexyl butyl acrylate, 3,4-epoxy cyclohexyl hex acrylate, etc. Oxiranyl group-containing (meth) acrylic compounds;

o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl 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- (acryloyloxymethyl) oxetane, 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 -3- (acryloyloxyalkyl) oxetanes such as phenyloxetane;

  3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -3-phenyloxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -3 -3- (methacryloyloxyalkyl) oxetanes such as phenyloxetane;

  2- (acryloyloxymethyl) oxetane, 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 -2- (acryloyloxyalkyl) oxetanes such as phenyloxetane;

2- (methacryloyloxymethyl) oxetane, 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 -Oxetanyl group containing (meth) acrylic compounds, such as 2- (methacryloyloxyalkyl) oxetanes, such as phenyl oxetane. The said epoxy group containing structural unit can be used individually or in combination of 2 or more types.

  Among the above epoxy group-containing monomers, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3- (methacryloyloxymethyl) -3-Methyloxetane and 3- (methacryloyloxymethyl) -3-ethyloxetane are preferable from the viewpoint of copolymerization reactivity with other radical polymerizable monomers and developability of the positive radiation sensitive composition.

  [A] The content of the epoxy group-containing structural unit in the polymer is not particularly limited as long as the desired heat resistance of the interlayer insulating film is exhibited, and the structural unit (1) and the epoxy group are contained in one polymer molecule. When the structural unit and the structural unit (2) are included, the monomer charge ratio is preferably 10% by mass or more and 60% by mass or less, and preferably 15% by mass or more with respect to all the structural units contained in the [A] polymer. 55 mass% or less is more preferable, and 20 mass% or more and 50 mass% or less are especially preferable.

  On the other hand, among the essential three structural units, when one polymer molecule has an epoxy group-containing structural unit alone or an epoxy group-containing structural unit and the structural unit (1) or the structural unit (2), the epoxy group-containing structure The content of the epoxy group-containing structural unit with respect to all the structural units contained in one polymer molecule having a unit is preferably 20% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 70% by mass in terms of monomer charge ratio. % Or less is more preferable, and 35 mass% or more and 65 mass% or less is especially preferable.

<Structural unit (2)>
[A] The polymer has a structural unit (2) containing a nitrogen-containing group in which the structure represented by the formula (II) is bonded to a nitrogen atom. The structural unit (2) is a structural unit derived from a monomer containing a nitrogen-containing group (hereinafter also referred to as “nitrogen group-containing monomer”). In the structural unit (2), deprotection of the nitrogen-containing group proceeds by the action of acid and heat during post-baking, and the crosslinking reaction of the epoxy group proceeds sufficiently by the exposed amine portion (nitrogen atom portion).

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁴ in the formula (II) include a methyl group, an ethyl group, a propyl group, an i-propyl group, an n-butyl group, and a t-butyl group. Can be mentioned. Examples of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms include cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, norbornyl group, tricyclodecyl group, tetracyclododecyl group, adamantyl group and the like. It is done.

Examples of the alkyl group having 1 to 4 carbon atoms and the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by R ⁵ and R ⁶ in the above formula (II) include R ^{4 in the} above formula (II). The definition of can be applied. Examples of the divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms formed together with the carbon atom to which R ⁵ and R ^{6 in} the formula (II) are bonded to each other include, for example, Examples thereof include a cyclobutanediyl group, a cyclopentanediyl group, a cyclohexanediyl group, a cyclooctanediyl group, a norbornanediyl group, a tricyclodecanediyl group, a tetracyclododecandiyl group, and an adamantanediyl group.

  The structural unit (2) is preferably a structural unit represented by the formula (2-1). Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by X in the formula (2-1) include a methylene group, an ethylene group, an n-propylene group, an i-propylene group, and an n-butylene group. , N-pentylene group, n-hexylene group, n-heptylene group, n-octylene group, n-nonylene group, n-decylene group, etc., bivalent linear or branched carbonization having 1 to 20 carbon atoms Hydrogen group; C 3-20 divalent such as cyclobutanediyl group, cyclopentanediyl group, cyclohexanediyl group, cyclooctanediyl group, norbornanediyl group, tricyclodecanediyl group, tetracyclododecanediyl group, adamantanediyl group, etc. An alicyclic hydrocarbon group; an arylene group having 6 to 20 carbon atoms such as a phenylene group or a naphthylene group; a benzylene group, a phenyleneethylene group, or a phenylenepropylene Group, naphthylene methylene group, such as arylenealkylene group having 7 to 20 carbon atoms, such as naphthylene ethylene group. Of these groups, groups having 2 or more carbon atoms are preferred.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ⁸ in the above formula (2-1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, 2- C1-C20 straight chain such as methylpropyl group, 1-methylpropyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group or the like Examples thereof include a branched alkyl group and groups exemplified in the description of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by R ⁴ in the above formula (II).

Examples of the heterocyclic structure having 4 to 20 carbon atoms formed by combining X and R ^{8 in} the above formula (2-1) with the nitrogen atom to which they are bonded include pyrrole, imidazole, pyrazole, and pyridine. , Pyridazine, pyrimidine, pyrazine, piperidine, pyrrolidine, piperazine, morpholine and the like. These structures may have a structure in which some hydrogen atoms are substituted with a linear or branched hydrocarbon group.

  Specific examples of the structure represented by the formula (II) include structures represented by the following formulas (II-1) to (II-21).

  As the structure represented by the above formula (II), a tert-butyloxycarbonyl group and a tert-amyloxycarbonyl group are preferable.

Preferable specific examples of the structural unit (2-1) include structural units represented by the following formulas (2-1-1) to (2-1-26). In the following formulae, R ⁷ has the same definition as in the above formula (2-1).

  [A] The content of the structural unit (2) in the polymer is not particularly limited as long as the [A] polymer is alkali-soluble by an acid and exhibits the desired heat resistance of the cured film. When the polymer molecule has the structural unit (1), the epoxy group-containing structural unit, and the structural unit (2), the monomer charge ratio is 3% by mass with respect to all the structural units contained in the [A] polymer. It is preferably 40% by mass or less, more preferably 5% by mass or more and 35% by mass or less, and particularly preferably 10% by mass or more and 30% by mass or less.

  On the other hand, among the essential three structural units, when one polymer molecule has the structural unit (2) alone, or the structural unit (2) and the structural unit (1) or the epoxy group-containing structural unit, the structural unit (2 The content of the structural unit (2) in the one polymer molecule having) is 10% by mass or more and 60% by mass or less in the monomer charge ratio with respect to all the structural units contained in the polymer molecule. 20 mass% or more and 55 mass% or less are more preferable, and 30 mass% or more and 50 mass% or less are especially preferable.

As the nitrogen group-containing monomer, a monomer having a (meth) acryloyl group corresponding to the target structural unit (2) can be suitably used. The method for synthesizing the nitrogen group-containing monomer giving the structural unit (2-1) can be synthesized according to the following procedure according to the following scheme.

  By stirring (meth) acrylic acid chloride and alcohol in a solvent such as tetrahydrofuran in the presence of an organic amine such as triethylamine, a nitrogen group-containing monomer and an organic amine hydrochloride can be obtained. The nitrogen group-containing monomer can be isolated by appropriately treating the reaction solution such as separation washing, distillation, and recrystallization. As a method not using acid chloride, an esterification reaction of alcohol using (meth) acrylic anhydride can also be used.

<Other structural units>
Examples of the radical polymerizable monomer that gives other structural units include a carboxyl group or a derivative thereof, a radical polymerizable monomer having a hydroxyl group, and the like.
Examples of the radical polymer 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 hexahydrophthal Acids, monocarboxylic acids such as 2-methacryloyloxyethyl hexahydrophthalic acid;
Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;
The acid anhydride of the said dicarboxylic acid etc. can be mentioned.

Examples of the radical polymerizable monomer having a hydroxyl group include
Acrylic acid hydroxyalkyl esters such as acrylic acid-2-hydroxyethyl ester, acrylic acid-3-hydroxypropyl ester, acrylic acid-4-hydroxybutyl ester, acrylic acid-4-hydroxymethylcyclohexylmethyl ester;
Methacrylic acid-2-hydroxyethyl ester, methacrylic acid-3-hydroxypropyl ester, methacrylic acid-4-hydroxybutyl ester, methacrylic acid-5-hydroxypentyl ester, methacrylic acid-6-hydroxyhexyl ester, methacrylic acid-4- Mention may be made of methacrylic acid hydroxyalkyl esters such as hydroxymethyl-cyclohexylmethyl ester.

  Among these radical polymerizable monomers having a hydroxyl group, acrylic acid-2-hydroxyethyl ester, from the viewpoint of copolymerization reactivity with other radical polymerizable monomers and heat resistance of the resulting interlayer insulating film, Acrylic acid-3-hydroxypropyl ester, acrylic acid-4-hydroxybutyl ester, methacrylic acid-2-hydroxyethyl ester, methacrylic acid-4-hydroxybutyl ester, acrylic acid-4-hydroxymethyl-cyclohexylmethyl ester, methacrylic acid -4-Hydroxymethyl-cyclohexylmethyl ester is preferred.

Examples of other radical polymerizable 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, acrylate-2-methylcyclohexyl, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, acrylate-2- (tricyclo [5.2.1.0 ^{2, 6} ] Acrylic alicyclic alkyl ester such as decan-8-yloxy) ethyl, isobornyl acrylate;
Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, methacrylic acid-2- (tricyclo [5.2.1.0 ^{2, 6} ] decano-8-yloxy) ethyl, methacrylic acid alicyclic alkyl esters such as isobornyl methacrylate;
Aryl esters of acrylic acid such as phenyl acrylate and benzyl acrylate and aralkyl esters of acrylic acid;
Aryl esters of methacrylic acid such as phenyl methacrylate and benzyl methacrylate and aralkyl esters of methacrylic acid;
Dicarboxylic acid dialkyl esters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Unsaturated 5-membered ring methacrylates and unsaturated 6-membered ring methacrylates 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 Unsaturated heterocyclic 5-membered methacrylates 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 esters 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;
Other unsaturated compounds such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride and vinyl acetate can be mentioned.

Among these other radical polymerizable monomers, styrene, 4-isopropenylphenol, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, tetrahydrofurfuryl methacrylate, 1, Radical polymerizability in which 3-butadiene, 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, N-cyclohexylmaleimide, N-phenylmaleimide, benzyl methacrylate, etc. have the above reactive functional groups It is preferable in terms of copolymerization reactivity with the monomer and developability of the positive radiation sensitive composition.

[A] The weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) by GPC (gel permeation chromatography) of the polymer is preferably 2.0 × 10 ^{3 to} 1.0 × 10 ⁵ , more preferably. It is 5.0 * 10 < ³ > -5.0 * 10 < ⁴ >. [A] By making Mw of a polymer into the said range, the radiation sensitivity and alkali developability of the said positive type radiation sensitive composition can be improved.

Moreover, the number average molecular weight (hereinafter referred to as “Mn”) in terms of polystyrene by GPC (gel permeation chromatography) of the [A] polymer is preferably 2.0 × 10 ^{3 to} 1.0 × 10 ⁵ . Preferably it is 5.0 * 10 < ³ > -5.0 * 10 < ⁴ >. By setting the Mn of the copolymer within the above range, the curing reactivity at the time of curing the coating film of the positive radiation sensitive composition can be improved.

  Furthermore, the molecular weight distribution “Mw / Mn” of the [A] 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 developability of the obtained interlayer insulating film can be improved. [A] The positive-type radiation-sensitive composition containing a polymer can easily form a desired pattern shape without causing a development residue during development.

<[A] Production method of polymer>
[A] The polymer can be produced by radical copolymerization of an acetal structure-containing monomer, an epoxy group-containing monomer, a nitrogen group-containing monomer, and other structural unit-derived monomers. When producing the [A] polymer having all of the structural unit (1), the epoxy group-containing structural unit and the nitrogen group-containing monomer in the same polymer molecule, at least an acetal structure-containing monomer and an epoxy group What is necessary is just to copolymerize using the mixture containing a monomer and a nitrogen-group containing monomer. On the other hand, for example, when the [A] polymer having the structural unit (1) and the structural unit (2) in one polymer molecule and the epoxy group-containing structural unit in a different polymer molecule is produced, A polymer solution having the structural unit (1) and the structural unit (2) is obtained by radical polymerization of a polymerizable solution containing at least an acetal structure-containing monomer and a nitrogen group-containing monomer, and at least an epoxy group is separately obtained. The polymerizable solution containing the containing monomer may be radically polymerized to obtain a polymer molecule having an epoxy group-containing structural unit, and finally both are mixed to form the [A] polymer.

  [A] Examples of the solvent used in the polymerization reaction for producing the polymer include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, and propylene glycol monoalkyls. Examples include ether acetate, propylene glycol monoalkyl ether propionate, aromatic hydrocarbons, ketones, and other esters.

These solvents include
Examples of alcohols include methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol and the like;
Ethers such as tetrahydrofuran;
Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
Examples of 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, diethylene glycol ethyl methyl ether and the like;
Examples of propylene glycol monoalkyl ethers 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;
As propylene glycol monoalkyl ether propionate, for example, 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, Methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3-hydroxypropionic acid Butyl, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate Methyl propoxyacetate, 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- Butyl toxipropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxy Examples include esters such as propyl propionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

  Among these solvents, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and butyl methoxyacetate are preferable, particularly diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate and butyl methoxyacetate are preferred.

[A] As the polymerization initiator used in the polymerization reaction for producing the polymer, those generally known as radical polymerization initiators can be used. Examples of radical polymerization initiators include:
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);
And organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) cyclohexane; and hydrogen peroxide.

  When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox initiator.

[A] In the polymerization reaction for producing the polymer, a molecular weight modifier can be used to adjust the molecular weight. Specific examples of molecular weight regulators include
Halogenated hydrocarbons such as chloroform and carbon tetrabromide;
mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid;
Xanthogens such as dimethylxanthogen sulfide and diisopropylxanthogen disulfide;
Examples include terpinolene and α-methylstyrene dimer.

<[B] Acid generator>
[B] The acid generator is a compound that generates an acid either by irradiation of radiation or by application of heat. Here, as the radiation, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used. By including the [A] polymer having an acid-dissociable group and the [B] acid generator, the positive radiation-sensitive composition can exhibit positive radiation-sensitive characteristics. [B] The acid generator is not particularly limited as long as it is a compound that generates an acid (for example, carboxylic acid, sulfonic acid, etc.) by irradiation with radiation or application of heat. [B] The inclusion form of the acid generator in the positive radiation-sensitive composition is also a form of an acid generator (hereinafter also simply referred to as “[B] acid generator”) which is a compound as described later. [A] It may be in the form of an acid generating group incorporated as part of a polymer or other polymer, or in both forms. In addition, whether to generate acid from the acid generator by irradiation of radiation or application of heat is determined by adjusting the temperature at the time of pre-bake before exposure, the irradiation dose, the temperature at the time of post-bake, etc. However, as the [B] acid generator, an acid generator that generates an acid by irradiation with radiation during exposure and generates an acid by heat during post-baking is preferable. By using such a [B] acid generator, the positive radiation-sensitive composition can exhibit positive radiation-sensitive characteristics, and at the time of post-baking, the structural unit (A) in the polymer ( The nitrogen-containing group contained in 2) can be deprotected to sufficiently advance the crosslinking reaction of the epoxy group.

  [B] The acid generator typically includes oxime sulfonate compounds, such as diphenyliodonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, ammonium salt, phosphonium salt, and tetrahydrothiophenium salt. Examples include onium salts, sulfonimide compounds, and quinonediazide compounds.

<Oxime sulfonate compound>
As said oxime sulfonate compound, the compound containing the oxime sulfonate group represented by following formula (3) is preferable.

In the above formula (3), R ^B1 is a linear, branched or cyclic alkyl group which may be substituted, or an aryl group which may be substituted. The alkyl group for R ^B1 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R ^B1 includes an alkoxy group having 1 to 10 carbon atoms or an alicyclic group (including a bridged alicyclic group such as a 7,7-dimethyl-2-oxonorbornyl group, preferably bicycloalkyl. Group) and the like. The aryl group for R ^B1 is preferably an aryl group having 6 to 11 carbon atoms, and more preferably a phenyl group or a naphthyl group. The aryl group of R ^B1 may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group, or a halogen atom.

  The compound containing an oxime sulfonate group represented by the above formula (3) is more preferably an oxime sulfonate compound represented by the following formula (4).

In the above formula ^{(4), R B1} has the same meaning as described for ^{R B1} in the formula (3). X is an alkyl group, an alkoxy group, or a halogen atom. m is an integer of 0-3. When m is 2 or 3, the plurality of X may be the same or different. The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

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

  Specific examples of the oxime sulfonate compound include, for example, compounds (4-i), (4-ii), (4-iii) represented by the following formulas (4-i) to (4-v), A compound (4-iv), a compound (4-v), etc. are mentioned.

  These can be used alone or in combination of two or more, and can also be used in combination with other acid generators as the component [B]. The said compounds (4-i)-(4-v) can be obtained as a commercial item.

<Onium salt>
Among the above onium salts, examples of diphenyliodonium salts 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-butyl) Phenyl) iodonium hexafluoroarsenate, bis (4-t-butylphenyl) iodo Umum trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium-p-toluenesulfonate, bis (4-t-butylphenyl) iodonium camphorsulfonic acid Etc.

  Examples of triphenylsulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, triphenyl Examples include sulfonium butyl tris (2,6-difluorophenyl) borate.

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

As these sulfonium salts,
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, etc .;
Examples of benzylsulfonium salts include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, and benzyl-4-methoxyphenylmethyl. Sulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethyl Sulfonium hexafluorophosphate, etc .;
Examples of the dibenzylsulfonium salt include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyl dibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexa Fluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4 -Hydroxyphenylsulfonium hexafluorophosphate and the like;
Examples of substituted benzylsulfonium salts include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and p-chlorobenzyl-4-hydroxyphenylmethylsulfonium. Hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro Examples include -4-hydroxyphenylmethylsulfonium hexafluoroantimonate.

  Examples of benzothiazonium salts include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p-methoxy Benzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, and the like.

  Examples of tetrahydrothiophenium salts include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 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, 2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydro Ofenium-2- (6-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (4,7-dibutoxy-1 -Naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate and the like.

  Among these onium salts, triphenylsulfonium salts, sulfonium salts, benzothiazonium salts, tetrahydrothiophenium salts from the viewpoint of improving the radiation sensitivity of the positive-type radiation-sensitive composition and the acid generation efficiency by heat application. Are preferably used. Among these, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium Hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexa Fluorophosphate, 1- (4-n-butoxynaphtha Down-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate are preferred.

<Sulfonimide compound>
Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide (trade name “SI-105” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) succinimide (trade name “SI-”). 106 "(manufactured by Midori Chemical Co., Ltd.)), N- (4-methylphenylsulfonyloxy) succinimide (trade name" SI-101 "(manufactured by Midori Chemical Co., Ltd.)), N- (2-trifluoromethylphenyl) Sulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide N- (2-fluoropheny Sulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide (trade name “PI-105” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) diphenylmaleimide, 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 (trade name “NDI-100” (manufactured by Midori Chemical Co., Ltd.)), N- (4 -Methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide (trade name "NDI-101" (manufactured by Midori Chemical Co., Ltd.)), N- (trifluoromethane Sulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide (trade name “NDI-105” (manufactured by Midori Chemical Co., Ltd.)), N- (nonafluorobutanesulfonyloxy) ) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide (trade name “NDI-109” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) ) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide (trade name “NDI-106” (manufactured by Midori Chemical Co., Ltd.)), 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-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2. .1] Hept-5-ene-2,3-dicarboximide, 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-fluorophenylsulfonyloxy) -7- Oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, 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-dicarboxylimide, 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 (trade name “NAI-105” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) naphthyl dicarboxylimide (trade name “NAI-106”) (Manufactured by Midori Chemical Co., Ltd.)), N- (4-methylphenylsulfonyloxy) naphthyl dicarboxylimide (trade name “NAI-101” (manufactured by Midori Chemical Co., Ltd.)), N- (phenylsulfonyloxy) naphthyl Dicarboxylimide (trade name “NAI-100” (manufactured by Midori Chemical Co., Ltd.)), N- (2-trifluoromethylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (4-fluorophenylsulfonyloxy) naphthyldi Carboxylimide, N- (pentafluoroethylsulfonyloxy ) Naphthyl dicarboxylimide, N- (heptafluoropropylsulfonyloxy) naphthyl dicarboxylimide, N- (nonafluorobutylsulfonyloxy) naphthyl dicarboxylimide (trade name “NAI-109” (manufactured by Midori Chemical Co., Ltd.)) N- (ethylsulfonyloxy) naphthyl dicarboximide, N- (propylsulfonyloxy) naphthyl dicarboximide, N- (butylsulfonyloxy) naphthyl dicarboximide (trade name “NAI-1004” (Midori Chemical Co., Ltd.) Manufactured)), N- (pentylsulfonyloxy) naphthyl dicarboxylimide, N- (hexylsulfonyloxy) naphthyl dicarboxylimide, N- (heptylsulfonyloxy) naphthyl dicarboxylimide, N- (octyl) Ruhoniruokishi) naphthyl dicarboxyl imide, N- (nonyl sulfonyloxy) naphthyl dicarboxylic imide and the like

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

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

As these mother cores,
Examples of trihydroxybenzophenone include 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone;
Examples of tetrahydroxybenzophenone include 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3, 4,2′-tetrahydroxy-4′-methylbenzophenone, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone, etc .;
Examples of pentahydroxybenzophenone include 2,3,4,2 ′, 6′-pentahydroxybenzophenone and the like;
Examples of hexahydroxybenzophenone include 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone and the like;

  Examples of (polyhydroxyphenyl) alkanes include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tris (p-hydroxyphenyl). ) Ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl-4) -Hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl- 4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiin Down -5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl -7,2 ', 4'-trihydroxy flavan like;

  As other mother nucleus, for example, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 1- [1- (3- {1- (4- Hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4, 6-dihydroxyphenyl) -1-methylethyl) benzene and 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene.

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

  The 1,2-naphthoquinone diazide sulfonic acid halide is preferably 1,2-naphthoquinone diazide sulfonic acid chloride. Specific examples of 1,2-naphthoquinone diazide sulfonic acid chloride include 1,2-naphthoquinone diazide-4-sulfonic acid chloride and 1,2-naphthoquinone diazide-5-sulfonic acid chloride. Among these, it is particularly preferable to use 1,2-naphthoquinonediazide-5-sulfonic acid chloride.

  Preferable examples of the condensate of a phenolic compound or alcoholic compound and 1,2-naphthoquinonediazide sulfonic acid halide include 1,1,1-tri (p-hydroxyphenyl) ethane and 1,2-naphthoquinonediazide-5. -Condensate with sulfonic acid chloride, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide-5 A condensate with sulfonic acid chloride is mentioned.

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

  Examples of the quinonediazide compound include 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, such as 2,3,4-triaminobenzophenone-1,2-naphthoquinonediazide- 4-sulfonic acid amide and the like are also preferably used. These [B] components can be used individually or in combination of 2 or more types.

  The content of the [B] acid generator in the positive radiation sensitive composition is preferably 1 to 20 parts by mass, more preferably 1 to 10 parts per 100 parts by mass of the [A] polymer. Part by mass. When the content of the component [B] is in the above range, the difference in solubility between the irradiated portion and the unirradiated portion in the alkaline aqueous solution serving as the developer is large, the patterning performance is improved, and the obtained interlayer insulating film The solvent resistance is also improved.

<Other optional components>
In addition to the above-mentioned [A] component and [B] component, the positive radiation-sensitive composition of the present invention includes [C] surfactant, [D] as necessary, within a range not impairing the intended effect. Other optional components such as an adhesion assistant and [E] basic compound can be contained.

<[C] Surfactant>
[C] Surfactant can be used for the positive radiation sensitive composition in order to further improve the coating property at the time of coating film formation. Examples of the surfactant that can be suitably used include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant.

  Examples of fluorosurfactants include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,1) 2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether and other fluoroethers; sodium perfluorododecylsulfonate; 1,1,2 , 2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexaph Fluoroalkanes such as orodecane; sodium fluoroalkylbenzenesulfonates; fluoroalkyloxyethylene ethers; fluoroalkylammonium iodides; fluoroalkylpolyoxyethylene ethers; perfluoroalkylpolyoxyethanols; perfluoroalkylalkoxylates And fluorine-based alkyl esters.

  Commercially available products of these fluorosurfactants include BM-1000, BM-1100 (manufactured by BM Chemie), MegaFack F142D, F172, F173, F183, F178, F191, F191, and F471. (Above, Dainippon Ink & Chemicals, Inc.), Florard FC-170C, FC-171, FC-430, FC-431 (above, Sumitomo 3M Limited), Surflon S-112, S-113 S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (Manufactured by Asahi Glass Co., Ltd.), Ftop EF301, 303, 352 (manufactured by Shin-Akita Kasei Co., Ltd.), and Fantent FTX-218 (manufactured by Neos Co., Ltd.) It is.

  Specific examples of the silicone-based surfactant include commercially available product names such as DC3PA, DC7PA, FS-1265, SF-8428, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SH 8400 FLUID, SZ-6032 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (above, GE Toshiba Silicone) For example).

  Nonionic surfactants include, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like. Polyoxyethylene aryl ethers; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; (meth) acrylic acid copolymers and the like. As a typical commercially available nonionic surfactant, Polyflow No. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.). These surfactants can be used alone or in combination of two or more.

  In the positive radiation sensitive composition, the [C] surfactant is preferably 0.05 parts by mass or more and 5 parts by mass or less, more preferably 0.1 parts by mass with respect to 100 parts by mass of the [A] polymer. It is used in an amount of 2 parts by mass or more and 2 parts by mass or less. [C] By making the usage-amount of surfactant into the said range, the film roughening at the time of forming a coating film on a board | substrate can be suppressed.

<[D] Adhesion aid>
In the positive-type radiation-sensitive composition, in order to improve the adhesion between an inorganic material serving as a substrate, for example, a silicon compound such as silicon, silicon oxide and silicon nitride, a metal such as gold, copper and aluminum, and an insulating film [ D] Adhesion aids that are components can be used. As such an adhesion assistant, a functional silane coupling agent is preferably used. Examples of functional silane coupling agents include silane coupling agents having reactive substituents such as carboxyl groups, methacryloyl groups, isocyanate groups, epoxy groups (preferably oxiranyl groups), thiol groups, and the like.

  Specific examples of functional silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxy Examples include propyltrimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. . Among these, γ-glycidoxypropylalkyldialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane are preferable.

  In the positive radiation sensitive composition, the [D] adhesion assistant is preferably 0.5 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass with respect to 100 parts by mass of the [A] polymer. It is used in an amount of no less than 10 parts and no more than 10 parts by mass. By setting the amount of the adhesion assistant in the above range, the adhesion between the formed interlayer insulating film and the substrate is improved.

<[E] basic compound>
The positive radiation sensitive composition may contain a basic compound as long as the effects of the present invention are not impaired. The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples of the basic compound include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, carboxylic acid quaternary ammonium salts, and the like. By containing a basic compound in the positive radiation-sensitive composition, the diffusion length of the acid generated from the acid generator by exposure can be appropriately controlled, and the pattern developability can be improved. it can.

  Primary aliphatic amines include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-amylamine, cyclopentylamine, Examples include hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine and the like.

  Secondary aliphatic amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, Examples include dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepentamine and the like.

  Tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, tri Hexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ′, N′-tetramethylmethylenediamine, N, N, Examples thereof include N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyltetraethylenepentamine and the like.

  Examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine, dicyclohexylmethylamine and the like.

  Aromatic amines and heterocyclic amines include aniline derivatives such as aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N, N-dimethyltoluidine, etc.), diphenylamine, diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (eg, pyrrole, 2H-pyrrole, 1-methylpyrrole, , 4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (eg oxazole, isoxazole etc.), thiazole derivatives (eg thiazole, isothiazole etc.), imidazole derivatives (eg imidazole, 4 -Methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, triphenylimidazole, etc.), pyrazole derivatives, furazane derivatives, pyrroline derivatives (eg pyrroline, 2-methyl-1-pyrroline etc.), Pyrrolidine derivatives (eg, pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (eg, pyridine, methylpyridine, Tylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 3-methyl-4-phenylpyridine, 4- tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) ) Pyridine, aminopyridine, dimethylaminopyridine, nicotine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazole derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives , Morpholine derivatives (eg morpholine, 4-methylmorpholine etc.), indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (eg quinoline, 3-quinolinecarbonitrile, 8-oxyquinoline etc.), isoquinoline Derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, Guanosine derivative, uracil derivative, uridine derivative, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.3.0] -7- Polycyclic amines such as Ndesen are exemplified.

  Examples of nitrogen-containing compounds having a carboxy group include aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (for example, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine, Phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine) and the like.

  Examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid and pyridinium p-toluenesulfonate.

  Examples of the nitrogen-containing compound having a hydroxy group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indolemethanol hydrate, mono Ethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4- Amino-1-butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) ethyl] piperazine The Lysine ethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8- Hydroxyurolidine, 3-cuincridinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide Etc. are exemplified.

  Examples of amide derivatives include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, nicotinic acid amide and the like.

  Examples of imide derivatives include phthalimide, succinimide, maleimide and the like.

  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.

  Furthermore, the basic compound represented by following formula (5) and (6) can also be mix | blended.

(In the formulas (5) and (6), R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁷ and R ⁴⁸ are each independently a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms. R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁹ and R ⁵⁰ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and some or all of the hydrogen atoms in the alkyl group may be substituted with an amino group. R ⁴⁴ and R ⁴⁵ , R ⁴⁵ and R ⁴⁶ , R ⁴⁴ and R ⁴⁶ , R ⁴⁴ and R ⁴⁵ and R ⁴⁶ , and R ⁴⁹ and R ⁵⁰ may be bonded to form a ring. , U are each an integer of 0 to 20. However, when all of S, T, and U are 0 at the same time, R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁹ , and R ⁵⁰ are all hydrogen atoms. Absent.)

In the above formulas (5) and (6), the alkylene group of R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁷ and R ⁴⁸ has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms. Is. Specifically, methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, n-pentylene group, isopentylene group, hexylene group, nonylene group, decylene group, cyclopentylene group, Examples thereof include a cyclohexylene group.

^The alkyl groups ^{R 44, R 45, R 46} , R 49, R 50, 1~20 carbon atoms, preferably 1 to 8, even more preferably 1 to 6, these linear , Either branched or annular. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, hexyl group, nonyl group, decyl group, dodecyl Group, tridecyl group, cyclopentyl group, cyclohexyl group and the like.

Further, when R ⁴⁴ and R ⁴⁵ , R ⁴⁵ and R ⁴⁶ , R ⁴⁴ and R ⁴⁶ , R ⁴⁴ and R ⁴⁵ and R ⁴⁶ , and R ⁴⁹ and R ⁵⁰ form a ring, the carbon number of the ring is typically It is 1-20, More preferably, it is 1-8, More preferably, it is 1-6, Moreover, the C1-C6, especially 1-4 alkyl group may branch these rings. S, T, and U are each an integer of 0 to 20, more preferably 1 to 10, and even more preferably an integer of 1 to 8.

  Specific examples of the compounds of the above formulas (5) and (6) include tris {2- (methoxymethoxy) ethyl} amine, tris {2- (methoxyethoxy) ethyl} amine, tris [2-{(2- Methoxyethoxy) methoxy} ethyl] amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} amine , Tris {2- (1-ethoxypropoxy) ethyl} amine, tris [2-{(2-hydroxyethoxy) ethoxy} ethyl] amine, 4,7,13,16,21,24-hexaoxa-1,10- Diazabicyclo [8.8.8] hexacosane, 4,7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] eicosane 1,4,10,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6, etc. Can be mentioned.

  In particular, [E] basic compounds include tertiary amines, aniline derivatives, pyrrolidine derivatives, pyridine derivatives, quinoline derivatives, amino acid derivatives, nitrogen-containing compounds having a hydroxy group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic properties Nitrogen-containing compounds, amide derivatives, imide derivatives, tris {2- (methoxymethoxy) ethyl} amine, tris {(2- (2-methoxyethoxy) ethyl} amine, tris [2-{(2-methoxyethoxy) methyl} Ethyl] amine, 1-aza-15-crown-5 and the like are preferable.

  It is preferable that content of the basic compound in the said positive radiation sensitive composition shall be 0.001-1 mass part with respect to 100 mass parts of [A] polymers, and 0.005-0.2 mass. More preferably, it is a part. Pattern developability becomes favorable by making content of a basic compound into the said range.

<Positive radiation sensitive composition>
The positive radiation-sensitive composition of the present invention is prepared by mixing the above-mentioned [A] polymer and [B] acid generator, and optional components as necessary. Usually, the positive radiation sensitive composition is preferably prepared and used in a state dissolved or dispersed in an appropriate [F] solvent. For example, a positive radiation-sensitive composition can be prepared by mixing [A] and [B] components and optional components in a solvent in a predetermined ratio.

<[F] solvent>
As the [F] solvent that can be used for the preparation of the positive radiation sensitive composition, those that uniformly dissolve or disperse each component and do not react with each component are preferably used. Examples of such solvents include alcohols, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionate. , Aromatic hydrocarbons, ketones, esters and the like.

These solvents include
Examples of alcohols include benzyl alcohol and diacetone alcohol;
Examples of ethers include dialkyl ethers such as tetrahydrofuran, diisopropyl ether, di n-butyl ether, di n-pentyl ether, diisopentyl ether, and di n-hexyl ether;
Examples of diethylene glycol alkyl ethers 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 ethylene glycol alkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate;
Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether;
Examples of propylene glycol monoalkyl ether acetates include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate;
Examples of propylene glycol monoalkyl ether propionates include propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate and the like;

Examples of aromatic hydrocarbons include toluene and xylene;
Examples of ketones include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone, etc.
Examples of esters include methyl acetate, ethyl acetate, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropionic acid Ethyl, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, protyl 3-hydroxypropionate, 3-hydroxy Butyl propionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, ethoxy Butyl acetate, methyl propoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propylbutoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2 Examples thereof include propyl methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate and the like.

  Among these solvents, from the viewpoint of excellent solubility or dispersibility, non-reactivity with each component, and ease of coating film formation, ethers such as dialkyl ethers, diethylene glycol alkyl ethers, Ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, ketones and esters are preferred, especially diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol Noethyl ether acetate, cyclohexanone, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl lactate, Ethyl lactate, propyl lactate, butyl lactate, methyl 2-methoxypropionate and ethyl 2-methoxypropionate are preferred. These solvents can be used alone or in combination.

  Among these solvents, ethers such as diisopropyl ether such as diisopropyl ether, di n-butyl ether, di n-pentyl ether, diisopentyl ether, and di n-hexyl ether are preferable, and diisopentyl ether is most preferable. . By using such a solvent, when applying the radiation-sensitive composition to a large glass substrate by the slit coating method, the drying process time is shortened, and at the same time, the coating property is further improved (coating unevenness is suppressed). Is possible.

  In addition to the above-mentioned solvents, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-octanol High-boiling solvents such as nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, carbitol acetate and the like can also be used in combination.

  When preparing a positive radiation-sensitive composition in the form of a solution or dispersion, the proportion of components other than the [F] solvent in the solution (that is, the total amount of the components [A] and [B] and other optional components) Can be arbitrarily set according to the purpose of use, desired film thickness and the like, but is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and further preferably 15 to 35% by mass.

<Formation of interlayer insulating film>
Next, a method for forming a cured film of an interlayer insulating film on a substrate using the positive radiation sensitive composition will be described. The method includes the following steps in the order described below.
(1) The process of forming the coating film of the said positive type radiation sensitive composition on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) A step of developing the coating film irradiated with radiation in the step (2), and (4) A step of heating the coating film developed in the step (3).

<(1) Step of forming a coating film of positive radiation sensitive composition on substrate>
In the step (1), after coating the positive radiation-sensitive composition solution or dispersion on the substrate, the coating surface is preferably removed by heating (pre-baking) the coated surface. Form. Examples of the substrate that can be used include a glass substrate, a quartz substrate, a resin substrate, and the like in addition to the substrate exemplified in [D] adhesion aid. Specific examples of the resin substrate include substrates formed of polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, cyclic olefin ring-opening polymer, and hydrogenated products thereof.

  The coating method of the composition solution or dispersion is not particularly limited, and an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or the like is employed. be able to. Among these coating methods, a spin coating method or a slit die coating method is preferable, and a slit die coating method is particularly preferable. Prebaking conditions vary depending on the type of each component, the blending ratio, and the like, but can be preferably about 70 to 120 ° C for about 1 to 10 minutes.

<(2) Step of irradiating at least part of the coating film>
In the step (2), at least a part of the formed coating film is exposed. In this case, when a part of the coating film is exposed, it is usually exposed through a photomask having a predetermined pattern. As the radiation used for exposure, the radiation used for the acid generator is suitable. Among these radiations, radiation having a wavelength in the range of 190 to 450 nm is preferable, and radiation containing ultraviolet light of 365 nm is particularly preferable.

The exposure amount in this step is preferably 300 to 5,000 J / m ² , more preferably 400 to 1 as a value obtained by measuring the intensity of radiation at a wavelength of 365 nm with an illuminometer (OAI model 356, manufactured by OAI Optical Associates Inc.). , 500 J / m ² .

<(3) Development process>
In the step (3), by developing the exposed coating film, 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 alkalis 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. be able to.

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

<(4) Heating process>
In the step (4), the patterned thin film is heated by using a heating device such as a hot plate or an oven, thereby deprotecting the nitrogen-containing group in the component [A] and curing the epoxy group thereby. Can be promoted to obtain a desired cured product. The heating temperature in this step is, for example, 120 to 250 ° C. Although heating time changes with kinds of heating apparatus, for example, when performing a heating process on a hotplate, it can be set to 30 to 90 minutes when performing a heating process in an oven. 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 interlayer insulating film can be formed on the surface of the substrate.

<Interlayer insulation film>
The film thickness of the interlayer insulating film thus formed is preferably 0.1 to 8 μm, more preferably 0.1 to 6 μm, and still more preferably 0.1 to 4 μm.

  The interlayer insulating film formed from the positive radiation-sensitive composition of the present invention satisfies the general required characteristics of transmittance and voltage holding ratio in a well-balanced manner, as will be apparent from the following examples. Excellent surface hardness and solvent resistance. Therefore, the interlayer insulating film is suitably used for display elements.

  The present invention will be described more specifically with reference to synthesis examples and examples. However, the present invention is not limited to the following examples.

Below, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer were measured by gel permeation chromatography (GPC) under the following conditions.
Apparatus: GPC-101 (made by Showa Denko KK)
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 Example>
[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, 5 parts by mass of methacrylic acid, 40 parts by mass of 1-ethoxyethyl methacrylate, 5 parts by mass of styrene, 30 parts by mass of glycidyl methacrylate, 20 parts by mass of the nitrogen group-containing monomer (1) and 3 parts by mass of α-methylstyrene dimer. After replacing the charged 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 polymer (A-1). The polystyrene equivalent weight average molecular weight (Mw) of the polymer (A-1) was 8,000. Moreover, the solid content concentration of the polymer solution obtained here was 32.7 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, 5 parts by weight of methacrylic acid, 40 parts by weight of tetrahydro-2H-pyran-2-yl methacrylate, 5 parts by weight of styrene, 30 parts by weight of glycidyl methacrylate, 20 parts by weight of nitrogen group-containing monomer (2), and α-methyl After 3 parts by mass of styrene dimer was charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-2). The polymer (A-2) had a weight average molecular weight (Mw) in terms of polystyrene of 8,000. Moreover, the solid content concentration of the polymer solution obtained here was 32.3 mass%.

[Synthesis Example 3]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (methyl 2-methylpropionate) and 200 parts by mass of propylene glycol monomethyl ether acetate. Subsequently, 47 parts by mass of 1-n-butoxyethyl methacrylate, 20 parts by mass of the nitrogen group-containing monomer (1), 23 parts by mass of benzyl methacrylate, and 10 parts by mass of methacrylic acid were charged and replaced with nitrogen. It was. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (a-1). The polymer (a-1) had a polystyrene equivalent weight average molecular weight (Mw) of 8,000. Moreover, the solid content concentration of the polymer solution obtained here was 30.8 mass%.

[Synthesis Example 4]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (methyl 2-methylpropionate) and 200 parts by mass of propylene glycol monomethyl ether acetate. Subsequently, 60 parts by mass of 1-benzyloxyethyl methacrylate, 36 parts by mass of the nitrogen group-containing monomer (1), and 4 parts by mass of methacrylic acid were charged and purged with nitrogen, and then gently stirring was started. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (a-2). The polymer (a-2) had a polystyrene equivalent weight average molecular weight (Mw) of 8,000. Moreover, the solid content concentration of the polymer solution obtained here was 31.6 mass%.

[Synthesis Example 5]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (methyl 2-methylpropionate) and 200 parts by mass of propylene glycol monomethyl ether acetate. Subsequently, 55 parts by mass of tetrahydro-2H-pyran-2-yl methacrylate, 37 parts by mass of the nitrogen group-containing monomer (2), and 8 parts by mass of methacrylic acid were charged and replaced with nitrogen, and then gently stirring was started. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (a-3). The polymer (a-3) had a weight average molecular weight (Mw) in terms of polystyrene of 9,000. Moreover, the solid content concentration of the polymer solution obtained here was 29.8 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, after 52 parts by mass of glycidyl methacrylate and 48 parts by mass of benzyl methacrylate were charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (aa-1). The polymer (aa-1) had a polystyrene equivalent weight average molecular weight (Mw) of 10,000. Moreover, the solid content concentration of the polymer solution obtained here was 32.3 mass%.

[Synthesis Example 7]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 45 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate, 45 parts by mass of benzyl methacrylate, and 10 parts by mass of methacrylic acid were charged and purged with nitrogen, and then gently stirred. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (aa-2). The polymer (aa-2) had a weight average molecular weight (Mw) in terms of polystyrene of 10,000. Moreover, the solid content concentration of the polymer solution obtained here was 33.2 mass%.

[Synthesis Example 8]
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, 35 parts by mass of 1-n-butoxyethyl methacrylate, 35 parts by mass of benzyl methacrylate, 10 parts by mass of the nitrogen group-containing monomer (1) and 20 parts by mass of glycidyl methacrylate were substituted with nitrogen, and then gently stirred. I started. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (aa-3). The polymer (aa-3) had a weight average molecular weight (Mw) in terms of polystyrene of 9,000. Moreover, the solid content concentration of the polymer solution obtained here was 32.7 mass%.

[Comparative synthesis example]
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, 5 parts by mass of methacrylic acid, 40 parts by mass of 1-ethoxyethyl methacrylate, 5 parts by mass of styrene, 40 parts by mass of glycidyl methacrylate, 10 parts by mass of 2-hydroxyethyl methacrylate, and 3 parts by mass of α-methylstyrene dimer were charged. After that, 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 polymer (A-1). The polymer (AA-1) had a polystyrene equivalent weight average molecular weight (Mw) of 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]
[B] Acid generation in the solution containing the polymer (A-1) obtained in Synthesis Example 1 as the polymer (amount corresponding to 100 parts by mass (solid content) of the polymer (A-1)) (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (“IRGACURE PAG 108” manufactured by Ciba Specialty Chemicals) as an agent, [C] interface 0.20 parts by mass of a silicone-based surfactant (“SH 8400 FLUID” manufactured by Toray Dow Corning Co., Ltd.) as an activator, and γ-glycidoxypropyltrimethoxysilane 3.0 as an adhesion aid A positive radiation-sensitive composition (S-1) was prepared by mixing parts by mass and filtering through a membrane filter having a pore size of 0.2 μm.

[Examples 2 to 10 and Comparative Examples 1 to 3]
A positive radiation-sensitive composition was prepared in the same manner as in Example 1 except that the types and amounts of each component were as described in Table 1.

The components used in each example and comparative example are listed below.
[Monomer of [A] component]
Nitrogen group-containing monomer (1) (corresponding to the structural unit represented by the above formula (2-1-14))

  Nitrogen group-containing monomer (2) (corresponding to the structural unit represented by the above formula (2-1-17))

[[B] component acid generator]
B-1: 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate B-2: benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate B-3: (5-propylsulfonyloxyimino -5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile ("IRGACURE PAG 103" manufactured by Ciba Specialty Chemicals)
B-4: (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (“IRGACURE PAG 108” manufactured by Ciba Specialty Chemicals)
B-5: (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (“IRGACURE PAG 121” manufactured by Ciba Specialty Chemicals)
B-6: (Camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (“CGI1380” manufactured by Ciba Specialty Chemicals)
B-7: (5-octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile (“CGI725” manufactured by Ciba Specialty Chemicals)

[[C] component surfactant]
C-1: Silicone-based surfactant (“SH 8400 FLUID” manufactured by Toray Dow Corning Co., Ltd.)
C-2: Fluorosurfactant ("Fergent FTX-218" manufactured by Neos Co., Ltd.)

[(D) component adhesion aid]
D-1: γ-glycidoxypropyltrimethoxysilane D-2: β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane D-3: γ-methacryloxypropyltrimethoxysilane

[Amine compound for comparative example]
Triethylamine

<Physical property evaluation>
Each positive radiation sensitive composition prepared as described above was used, and the composition and various properties as a coating film or an interlayer insulating film were evaluated as follows.

(1) Evaluation of radiation sensitivity of radiation-sensitive composition Hexamethyldisilazane (HMDS) was applied on a 550 × 650 mm chromium-deposited glass and heated at 60 ° C. for 1 minute (HMDS treatment). The radiation-sensitive composition prepared as described above is applied onto the chromium-deposited glass after the HMDS treatment using a slit die coater “TR6321055-CL”, the ultimate pressure is set to 100 Pa, and the solvent is removed under vacuum. Then, the film was further pre-baked at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. Subsequently, using an MPA-600FA exposure machine manufactured by Canon Inc., the coating film was irradiated with radiation through the mask having a 60 μm line and space (10 to 1) pattern with the exposure amount as a variable. After that, the film was developed with a 0.4 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. This value is shown in Table 1 as radiation sensitivity. It can be said that the sensitivity is good when this value is 600 J / m ² or less.

(2) Evaluation of transmittance A coating film was formed on a silicon substrate in the same manner as in the above “(1) Evaluation of radiation sensitivity of radiation-sensitive composition”. Without being exposed, this silicon substrate was heated in a clean oven at 220 ° C. for 1 hour to obtain a cured film. The transmittance at a wavelength of 400 nm was measured and evaluated using a spectrophotometer (150-20 type double beam (manufactured by Hitachi, Ltd.)). At this time, it can be said that the transparency is poor when the transmittance is less than 90%. The evaluation results are shown in Table 1.

(3) Evaluation of surface hardness About the board | substrate which has the cured film formed in said "(2) Evaluation of transmittance", the pencil hardness of a cured film is carried out by the 8.4.1 pencil scratch test of JISK-5400-1990. (Surface hardness) was measured. When this value is 3H or larger, the surface hardness as an interlayer insulating film is good, and it can be said that the composition used for forming the cured film has sufficient curability. The evaluation results are shown in Table 1.

(4) Evaluation of solvent resistance About the board | substrate which has a cured film formed by said "(2) Evaluation of the transmittance | permeability", the film thickness (T1) of the obtained cured film was measured. And after immersing the silicon substrate in which this cured film was formed in the dimethylsulfoxide temperature-controlled at 70 degreeC for 20 minutes, the film thickness (t1) of the cured film was measured, and the film thickness change rate by immersion {(T1-T1) / T1} × 100 [%] was calculated. It can be said that the solvent resistance is excellent when the absolute value of this value is less than 5%. The results are shown in Table 1.

(5) Evaluation of voltage holding ratio The liquid feeling prepared on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed on the surface, and an ITO (indium-tin oxide alloy) electrode was deposited in a predetermined shape. After spin coating the radiation composition, 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, post-baking was performed at 230 ° C. for 30 minutes to cure the coating film to form a permanent cured film.

  Next, the substrate on which this pixel is 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 a liquid crystal MLC6608 (trade name) manufactured by Merck is used. The liquid crystal cell was manufactured by pouring. Furthermore, the liquid crystal cell was put in a constant temperature layer of 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” (trade name) manufactured by Toyo Corporation. The applied voltage at this time is a square wave of 5.5 V, and the measurement frequency is 60 Hz. The evaluation results are shown in Table 1.

  Here, the voltage holding ratio (%) is a value obtained from an equation of (liquid crystal cell potential difference after 16.7 milliseconds / voltage applied at 0 milliseconds) × 100. When 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".

(6) Evaluation of storage stability The radiation-sensitive composition solution was left in an oven at 40 ° C. for 1 week, and the viscosity before and after placing in the oven was measured to determine the rate of change in viscosity. At this time, when the viscosity change rate is 5% or less, the storage stability is good, and when it exceeds 5%, the storage stability is poor. The viscosity was measured at 25 ° C. using an E-type viscometer (trade name “VISCONIC ELD.R”, manufactured by Toki Sangyo Co., Ltd.). The evaluation results are shown in Table 1.

  As is clear from the results of Table 1, the positive radiation sensitive compositions of Examples 1 to 10 containing the components [A] and [B] are comparative examples in which the structural unit constituting the polymer does not contain a nitrogen-containing group Compared with the radiation sensitive compositions of Examples 1 to 3, it was found that the surface hardness and solvent resistance were excellent. In addition, the positive-type radiation-sensitive compositions of these examples form an interlayer insulating film having excellent storage stability and sufficient radiation sensitivity, as well as general required characteristics of transmittance and voltage holding ratio. I found it possible. In addition, in the comparative example, when an amine compound is added to increase the surface hardness and solvent resistance, the storage stability of the composition is lowered, and both the improvement of the surface hardness and the solvent resistance and the improvement of the storage stability are I could n’t.

  As described above, the positive radiation-sensitive composition of the present invention has excellent storage stability and sufficient radiation sensitivity, has general required characteristics of transmittance and voltage holding ratio, and has an excellent surface. A cured film having hardness and solvent resistance can be formed. Therefore, the positive radiation sensitive composition is suitably used for forming an interlayer insulating film for a display element.

Claims (5)

[A] In the same or different polymer molecules, a structural unit (1) containing a group represented by the following formula (I), an epoxy group-containing structural unit, and a structure represented by the following formula (II) A positive radiation-sensitive composition containing a polymer having a structural unit (2) containing a bonded group, and [B] an acid generator.

(In Formula (I), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and one of the hydrogen atoms of these alkyl group, cycloalkyl group, or aryl group) Part or all may be substituted with a substituent (provided that R ¹ and R ² are not both hydrogen atoms) R ³ represents an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, or — A group represented by M (R ^3m ) ₃ (M is Si, Ge or Sn, R ^3m is an alkyl group), and some or all of these hydrogen atoms are substituted with substituents; R ¹ and R ³ may be linked to form a cyclic ether.)

(In the formula (II), R ⁴ is an alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms. R ⁵ and R ⁶ are each independently An alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or R ⁵ and R ⁶ are bonded to each other, and carbon together with the carbon atom to which they are bonded (Forms a divalent alicyclic hydrocarbon group of formula 4 to 20. * is a bond bonded to a nitrogen atom.) The positive radiation sensitive composition according to claim 1, wherein the structural unit (2) is a structural unit represented by the following formula (2-1).

(In Formula (2-1), the definitions of R ⁴ , R ⁵ and R ⁶ are the same as those in Formula (II) above. R ⁷ is a hydrogen atom or a methyl group, and X is 2 having 1 to 20 carbon atoms. R ⁸ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and X and R ⁸ are bonded to each other, together with the nitrogen atom to which they are bonded, 4 to 20 heterocyclic structures may be formed.)   The positive radiation-sensitive composition according to claim 1 or 2, which is used for forming an interlayer insulating film of a display element. (1) The process of forming the coating film of the positive radiation sensitive composition of Claim 3 on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) A step of developing the coating film irradiated with radiation in step (2), and (4) A step of heating the coating film developed in step (3).   The interlayer insulation film of the display element formed from the positive radiation sensitive composition of Claim 3.