KR101396265B1 - Positive radiation-sensitive composition, interlayer insulating film for display element, and formation method for same - Google Patents

Abstract

(A) a polymer comprising a structural unit (I) having a group represented by the following formula (1) and an epoxy group-containing structural unit (II) in the same or different polymer molecules, [B] ] A positive radiation-sensitive composition containing at least one nitrogen-containing compound selected from the group consisting of a nitrogen-containing compound represented by the following formula (2) and a nitrogen-containing compound represented by the following formula (3) At least one group selected from the group consisting of R ⁶ in the formula (2) and R ⁹ and R ¹⁰ in the formula (3) is a tert-butyl group, a tert-amyl group, Cyclohexyl group or 1-ethylcyclohexyl group.

Description

TECHNICAL FIELD [0001] The present invention relates to a positive radiation-sensitive composition, a positive-ion radiation-sensitive composition, a display element interlayer insulating film and a method for forming the same.

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

In the display element, an interlayer insulating film is formed for the purpose of insulating between wirings generally arranged in layers. As a material for forming the interlayer insulating film, a positive radiation-sensitive composition is widely used because it is preferable that the number of steps for obtaining a necessary pattern shape is small and furthermore, it is desired to have sufficient flatness. The positive radiation-sensitive composition used for 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 the positive-tone radiation-sensitive composition, an acrylic resin is widely used, and for example, a resin having a structural unit containing an acid-cleavable group is reacted with a resin or a carboxyl group which becomes alkali-soluble when the acid- A positive radiation-sensitive composition containing a resin having a structural unit containing a functional group (such as an epoxy group) and an acid generator has been proposed (see JP-A-2009-98673). In this composition, the above-mentioned two kinds of specific resins are mixed, and in the coating film formed by using the above-mentioned composition, a carboxyl group produced by the action of an acid from a resin having a structural unit containing an acid-cleavable group, A curing reaction is carried out by a cross-linking reaction with a resin having a structural unit. However, due to the insufficient progress of the crosslinking reaction, the surface hardness and heat resistance of the obtained cured film are not satisfactory.

With respect to such a phenomenon, it is also possible to consider a method for advancing the crosslinking reaction by adding an amine compound used as a curing agent of an epoxy-based material. However, as for the addition of a common amine compound, a reaction with a epoxy group The storage stability may be lowered.

Therefore, it is conceivable that the amine compound is protected by protecting groups cleaved from the acid to lower the reactivity, thereby securing the storage stability of the composition. In addition, when the protecting group is removed by an acid generated in the process of forming a cured film, the amine compound can be provided for the crosslinking reaction with the epoxy group. However, the reaction in which the alkali-insoluble resin becomes alkali-soluble by the dissociation of the acid-dissociable group and the cross-linking reaction by the amine compound of the epoxy group proceed simultaneously, and the composition may not exhibit the positive radiation-sensitive characteristics.

Japanese Laid-Open Patent Publication No. 2009-98673

An object of the present invention is to provide a display element interlayer insulating film which is excellent in surface hardness and heat resistance and satisfies transmittance and voltage holding ratio which are general required characteristics, A positive radiation-sensitive composition having excellent radiation sensitivity and sufficient radiation sensitivity, an interlayer insulating film for a display element formed from the composition, and a method of forming the same.

According to an aspect of the present invention,

(A) a polymer containing a structural unit (I) having a group represented by the following formula (1) and an epoxy group-containing structural unit (II) in the same or different polymer molecules (hereinafter also referred to as "

[B] Arrhythmia, and

[C] at least one nitrogen-containing compound selected from the group consisting of a nitrogen-containing compound (I) represented by the following formula (2) and a nitrogen-containing compound (II) represented by the following formula (3) Nitrogen-containing compound ") is a positive-tone radiation-sensitive composition containing:

(In the formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, with the proviso that some or all of the hydrogen atoms of the alkyl group, cycloalkyl group and aryl group are substituted even good; also, R ¹ and R ² both are not a hydrogen atom; R ³ is an alkyl group, cycloalkyl group, aralkyl group, aryl group, or -M (R ^3m) group represented by _3; M is yi, Si, Ge or Sn; R ^3m each independently represents an alkyl group; and R ¹ and R ³ may be connected to form a cyclic ether structure, provided that some or all of the hydrogen atoms of these groups represented by R ³ May be substituted);

(Wherein R ⁴ and R ⁵ are each independently a hydrogen atom, an amino group, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, provided that the alkyl group and the aryl group each have a hydroxyl group, R ⁶ may be an alkyl group having 1 to 20 carbon atoms, an alkyl group having 4 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a carboxyl group, a carbonyl group, an ester group, a sulfone group, an amide group, an ether group, a thiol group, A cycloalkyl group or an aryl group having 6 to 20 carbon atoms, provided that R ⁴ and R ⁵ may form a cyclic structure together with the nitrogen atom to which they are bonded to each other;

(In the formula (3), R ⁷ and R ⁸ are each independently the same as R ⁴ , R ⁹ and R ¹⁰ are each independently the same as R ⁶ , A is a C 1-12 An alkanediyl group having 6 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms).

In the positive-tone radiation-sensitive composition, since a specific [C] nitrogen-containing compound having a carbamate structure is introduced by introducing a protecting group into a nitrogen atom portion as an amine compound, the [C] nitrogen- The reactivity can be suppressed, and the storage stability of the composition can be improved. Further, by employing a specific carbamate structure as the protective form of the [C] nitrogen-containing compound, the activation energy for deprotection is higher than the activation energy for dissociation of the group represented by the formula (1) . As a result, the [C] nitrogen-containing compound is not deprotected by the acid generated from the [B] acidogenic organism at the time of exposure, and the heat during post-baking after development and the co- And is deprotected by the action. Thus, in the positive-tone radiation-sensitive composition, not only a positive radiation-sensitive characteristic can be exhibited in a series of steps from exposure to development, but also the sensitivity of the epoxy group The crosslinking reaction can be sufficiently promoted and a cured film as an interlayer insulating film having excellent surface hardness and heat resistance can be formed.

At least one group selected from the group consisting of R ⁶ in the formula (2) and R ⁹ and R ¹⁰ in the formula (3) is a tert-butyl group, a tert-amyl group, Cyclohexyl group or 1-ethylcyclohexyl group. Thus, not only the reactivity control of the [C] nitrogen-containing compound is facilitated, but also the activation energy for deprotection of the [C] nitrogen-containing compound becomes appropriate, thereby protecting the acid from the acidogenic organism upon exposure, It is possible to exhibit a good deacidifying ability by heat and acid at the time of baking in a well-balanced manner.

The content of the [C] nitrogen-containing compound is preferably 2 parts by mass or more and 30 parts by mass or less based on 100 parts by mass of the polymer [A]. By setting the content of the [C] nitrogen-containing compound within the above-specified range, the crosslinking reaction of the epoxy group can be sufficiently advanced, and a side reaction with an unexpected epoxy group due to an excessive amount can be prevented, and the radiation of the positive radiation- Deterioration of sensitivity and storage stability and deterioration of transmittance and voltage holding ratio of the resulting cured film can be prevented.

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

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

(1) a step of forming a coating film of the positive radiation-sensitive composition on a substrate,

(2) a step of irradiating at least a part of the coating film with radiation,

(3) a step of developing the coating film irradiated with the radiation, and

(4) heating the developed coating film.

By the forming method of the present invention using the positive-tone radiation-sensitive composition, an interlayer insulating film for a display element which is excellent in surface hardness and heat resistance and sufficiently satisfies a transmittance and a voltage holding ratio can be formed.

As described above, the positive-tone radiation-sensitive composition of the present invention contains the [A] polymer, the [B] acidogenic organometallic compound and the [C] nitrogen-containing compound in a balanced manner so as to satisfy the general required characteristics of transmittance and voltage holding ratio In addition, an interlayer insulating film for a display element having excellent surface hardness and heat resistance can be formed. In addition, the positive radiation-sensitive composition has excellent storage stability and exhibits sufficient radiation sensitivity.

(Mode for carrying out the invention)

≪ Positive radiation sensitive composition >

The positive radiation-sensitive composition of the present invention contains the [A] polymer, the [B] acidogenic organism and the [C] nitrogen-containing compound. Further, the positive-tone radiation-sensitive composition may contain [D] a surfactant and [E] adhesion aid as suitable components. In addition, as long as the effect of the present invention is not impaired, other optional components may be contained. Hereinafter, each component will be described in detail.

<[A] Polymer>

The polymer [A] includes the structural unit (I) and the epoxy group-containing structural unit (II) in the same or different polymer molecules. In addition, other structural units may be included if necessary. Examples of the polymer [A] containing the structural unit (I) and the epoxy group-containing structural unit (II) are not particularly limited,

(i) contains both a structural unit (I) and an epoxy group-containing structural unit (II) in the same polymer molecule, and [A] when one kind of polymer molecule is present in the polymer;

(Ii) an epoxy group-containing structural unit (II) is contained in one polymer molecule, and the epoxy group-containing structural unit (II) is contained in a polymer molecule different from the structural unit ;

(Iii) contains not only structural unit (I) and epoxy group-containing structural unit (II) in one polymer molecule but also structural unit (I) in a different polymer molecule, Containing structural unit (II) in the molecule, and [A] when three kinds of polymer molecules are present in the polymer;

(Iv) a case in which, in addition to the polymer molecules defined in (i) to (iii), one or more other polymer molecules are contained in the polymer [A]. In either case, the effects of the present invention can be exhibited. The polymer [A] may contain two or more structural units. Hereinafter, each structural unit will be described in detail.

[Structural unit (I)]

In the structural unit (I), since the group represented by the formula (1) is present as a group (acid-cleavable group) dissociated in the presence of an acid to generate a polar group, As a result, the polymer [A] which was alkali-insoluble becomes alkali-soluble. The acid-dissociable group has a relatively stable acetal structure or ketal structure with respect to alkali, and these acid dissociable groups are dissociated by the action of an acid.

In the formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. However, some or all of the hydrogen atoms of the alkyl group, cycloalkyl group and aryl group may be substituted. In addition, R ¹ and R ² are not both hydrogen atoms. R ³ is 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 each independently represents an alkyl group. R ¹ and R ³ may be connected to form a cyclic ether structure. Provided that some or all of the hydrogen atoms of these groups represented by R &lt; ³ &gt; may be substituted.

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

Examples of the cycloalkyl group represented by R ¹ and R ² include a cycloalkyl group having 3 to 20 carbon atoms. The cycloalkyl group having 3 to 20 carbon atoms may be a polycyclic ring or may have an oxygen atom in the ring. Examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a boronyl group, a norbornyl group and an adamantyl group.

Examples of the aryl group represented by R ¹ and R ² include an aryl group having 6 to 14 carbon atoms. The aryl group having 6 to 14 carbon atoms may be monocyclic or monocyclic, or may be a condensed ring. Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group.

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

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

Examples of the group represented by -M (R ^3m ) ₃ include a trimethylsilanyl group, a trimethylgermyl group, and the like. As the substituent which may partially or wholly replace the hydrogen atom of the aralkyl group represented by R ³ or the group represented by -M (R ^3m ) ₃ , the substituent may be suitably employed. As the substituent of this group, for example, the groups exemplified as the substituents of the optionally substituted alkyl, cycloalkyl and aryl groups represented by R ¹ and R ² above may be applied.

Examples of the group having a cyclic ether structure which may be formed by connecting R ¹ and R ³ include a 2,2-oxetanediyl group, a 2,2-tetrahydrofuranyldihyl group, a 2-tetrahydropyranediyl group, And 2-dioxanediyl group.

The structural unit (I) may have an acetal structure or a ketal structure by having a functional group that has an acetal structure or a ketal structure by bonding to another carbon atom.

Examples of the functional group having an acetal structure by bonding to other carbon atoms include 1-methoxyethoxy group, 1-ethoxyethoxy group, 1-n-propoxyethoxy group, 1-i-propoxy Butoxyethoxy group, 1-t-butoxyethoxy group, 1-cyclopentyloxyethoxy group, 1-n-butoxyethoxy group, 1-cyclohexyloxyethoxy group, 1-norbornyloxyethoxy group, 1-boronyloxyethoxy group, 1-phenyloxyethoxy group, 1- (1-naphthyloxy) ethoxy group (Cyclohexyl) (n-propoxy) methoxy group, (cyclohexyl) (n-propoxy) (Cyclohexyl) (phenoxy) methoxy group, (cyclohexyl) (cyclohexyloxy) methoxy group, (cyclohexyl) (phenoxy) , (Phenyl) (methoxy) methoxy group, (phenyl) (ethoxy (Phenyl) (phenoxy) methoxy group, (phenyl) (n-propoxy) methoxy group, (Benzyl) (n-propoxy) methoxy group, (benzyl) (methoxy) methoxy group, (benzyl) (ethoxy) (Benzyl) (benzyloxy) methoxy group, 2-tetrahydrofuranyloxy group, 2-tetrahydropyranyloxy group, benzyloxy group, 1-trimethylsilanyloxyethoxy group, 1-trimethylgermyloxyethoxy group, and the like.

Among them, 1-ethoxyethoxy group, 1-cyclohexyloxyethoxy group, 2-tetrahydrofuranyloxy group, 1-n-propoxyethoxy group and 2-tetrahydropyranyloxy group are preferable.

Methyl-1-methoxyethoxy group, 1-methyl-1-ethoxyethoxy group, 1-methyl-1-n Propoxyethoxy group, 1-methyl-1-i-butoxyethoxy group, 1-methyl-1-i-butoxyethoxy group, 1 Methyl-1-cyclopentyloxyethoxy group, 1-methyl-1-cyclohexyloxy group, 1-methyl-1-cyclopentyloxyethoxy group, Methyl-1-norbornyloxyethoxy group, 1-methyl-1-bornyloxyethoxy group, 1-methyl- Methyl-1-benzyloxyethoxy group, 1-cyclohexyl-1-methoxyethoxy group, 1-cyclohexyl 1-cyclohexyl-1-cyclohexyloxy, 1-cyclohexyl-1-cyclohexyl-1-n-propoxyethoxy group, Toxic Cyclohexyl-1-phenoxyethoxy group, 1-cyclohexyl-1-benzyloxyethoxy group, 1-phenyl-1-methoxyethoxy group, 1-phenyl-1-ethoxyethoxy group 1-phenyl-1-cyclohexyloxyethoxy group, 1-phenyl-1-n-propoxyethoxy group, 1-benzyl-1-ethoxyethoxy group, 1-benzyl-1-n-propyloxy group, Benzyl-1-i-propoxyethoxy group, 1-benzyl-1-cyclohexyloxyethoxy group, 1-benzyl-1-phenyloxyethoxy group, 1-benzyl- (2-methyl-tetrahydropyranyl) oxy group, a 1-methoxy-cyclopentyloxy group, a 1-methoxy -Cyclohexyloxy group and the like.

Of these, 1-methyl-1-methoxyethoxy group and 1-methyl-1-cyclohexyloxyethoxy group are preferable.

Examples of the structural unit (I) having an acetal structure or a ketal structure include structural units represented by the following formulas (1-1) to (1-3).

In the formulas (1-1) to (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 formula (1).

Examples of the monomer giving the structural unit (I) represented by the above formulas (1-1) to (1-3)

(Meth) acrylate, 1- (cycloalkyloxy) alkyl (meth) acrylate, 1- (haloalkoxy) , (Meth) acrylate-based acetal structure-containing monomers such as tetrahydropyranyl (meth) acrylate;

Carbonyl) -5-norbornene, 2,3-di (1- (trialkylsilyloxy) alkoxy) carbonyl) Norbornene, 2,3-di (1-alkoxyalkoxycarbonyl) -5-norbornene, 2,3-di (1- (cycloalkyloxy) alkoxycarbonyl) Norbornene-based acetal structure-containing monomers such as 3-di (1- (aralkyloxy) alkoxycarbonyl) -5-norbornene;

Monomers containing a styrenic acetal structure such as 1-alkoxyalkoxystyrene, 1- (haloalkoxy) alkoxystyrene, 1- (aralkyloxy) alkoxystyrene, and tetrahydropyranyloxystyrene.

Of these, 1-alkoxyalkyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, 1-alkoxyalkoxystyrene and tetrahydropyranyloxystyrene are preferable, and 1-alkoxyalkyl (meth) desirable.

Specific examples of the monomer giving the structural unit (I) represented by the above formulas (1-1) to (1-3)

Methoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 1-isobutoxyethyl methacrylate, 1-t-butoxyethyl methacrylate, 1-ethoxyethyl methacrylate, 1- (2-ethylhexyloxy) ethyl methacrylate, 1-n-propoxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, 1 Methacrylate-based acetal structure-containing monomers such as - (2-cyclohexylethoxy) ethyl methacrylate, 1-benzyloxyethyl methacrylate, and 2-tetrahydropyranyl methacrylate;

Methoxyethyl acrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl acrylate, 1-t-butoxyethyl acrylate, 1- (2- Ethyl acrylate, 1-n-propyl acrylate, 1-cyclohexyloxyethyl acrylate, 1- (2-cyclohexylethoxy) Acrylate-based acetal structure-containing monomers such as ethyl acrylate, 1-benzyloxyethyl acrylate and 2-tetrahydropyranyl acrylate;

(1- (trimethylsilyloxy) 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) Norbornene-based acetal structure-containing monomers such as 2,3-di (1- (benzyloxy) ethoxycarbonyl) -5-norbornene;

p or m-1-ethoxyethoxystyrene, p or m-1-methoxyethoxystyrene, p or m-1-n-butoxyethoxystyrene, p or m-1-isobutoxyethoxystyrene, p or m-1- (2-chloroethoxy) ethoxystyrene, p or m-1- (1-dimethylethoxy) ethoxystyrene, P or m-1-n-propoxyethoxystyrene, p or m-1-cyclohexyloxyethoxystyrene, p or m-1- (2-cyclohexylethoxy) ethoxystyrene, p Or m-1-benzyloxyethoxystyrene; and the like. These monomers may be used alone or in combination of two or more.

Examples of the monomer giving the structural unit (I) include 1-ethoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 2-tetrahydropyranyl methacrylate, 1-benzyloxyethyl methacrylate The rate is preferred.

As the monomer giving the structural unit (I), commercially available monomers may be used, and those synthesized by known methods may be used. For example, the monomer giving the structural unit (I) represented by the formula (1-1) can be synthesized by reacting (meth) acrylic acid with a vinyl ether in the presence of an acid catalyst as shown in the following formula.

In the above formula, R ', R ¹ and R ³ have the same meanings as in the above formula (1-1). R ²¹ and R ²² are -CH (R ²¹ ) (R ²² ) and have the same meanings as R ² in the formula (1-1).

The content of the structural unit (I) in the polymer [A] is not particularly limited as long as the polymer [A] exhibits alkali solubility by the acid and exhibits the desired heat resistance of the cured film, Is preferably 5 mass% or more and 70 mass% or less, and more preferably 10 mass% or more, based on the total structural units contained in the polymer (A), in the case of containing both the structural unit (I) More preferably 60 mass% or less, and particularly preferably 20 mass% or more and 50 mass% or less.

On the other hand, in the case where one polymer molecule contains a structural unit (I) and a polymer molecule different therefrom contains an epoxy group-containing structural unit (II), in the one polymer molecule having the structural unit (I) , The content of the structural unit (I) in the polymer molecule is preferably 40 mass% or more and 99 mass% or less, more preferably 50 mass% or more and 98 mass% or less, with respect to the total structural units contained in the polymer molecule , And particularly preferably from 55 mass% to 95 mass%.

[Epoxy group-containing structural unit (II)]

The epoxy group-containing structural unit (II) is not particularly limited as long as it is a structural unit derived from an epoxy group-containing monomer. By including the epoxy group-containing structural unit (II) in the molecule of the polymer [A], the surface hardness and heat resistance of the cured film obtained from the positive radiation sensitive composition can further be enhanced. The epoxy group in the present specification is a concept including an oxiranyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure).

As the monomer giving the epoxy group-containing structural unit (II), for example,

(Meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 3-methyl-3,4-epoxybutyl acrylate, 3-ethyl- , 6-epoxyhexyl methacrylate, 5-methyl-5,6-epoxyhexyl methacrylate, 5-ethyl-5,6-epoxyhexyl methacrylate, 6,7-epoxyhexyl methacrylate, methacrylic acid, 4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl methacrylate, 3,4- Epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylethyl acrylate, 3,4-epoxycyclohexylpropyl acrylate, acrylic acid 3, 3-epoxycyclohexylmethyl acrylate, , 4-epoxycyclohexylbutyl, and 3,4-epoxycyclohexylhexyl acrylate (meth) acrylate-containing .;

o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether,? -methyl-o-vinyl benzyl glycidyl ether,? -methyl- Vinyl benzyl glycidyl ethers such as diester,? -Methyl-p-vinylbenzyl glycidyl ether;

vinylphenyl glycidyl ethers such as o-vinylphenyl glycidyl ether, m-vinylphenyl glycidyl ether and p-vinylphenyl glycidyl ether;

3-acryloyloxymethyl-3-ethyloxetane, 3-acryloyloxymethyl-3-phenyloxane, 3-acryloyloxymethyl- Cetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) -3-methyloxetane, 3- Cetyl, 3-methacryloyloxymethyloxetane, 3-methacryloyloxymethyl-3-methyloxetane, 3-methacryloxypropyltrimethoxysilane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- 3-methyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) Acryloyloxymethyl-2-ethyloxetane, 2-acryloyloxymethyl-2-phenyloxetane, 2-acryloyloxymethyl-2-methyloxetane, 2- 2- (2- Acryloyloxyethyl) oxetane, 2- (2-acryloyloxyethyl) -2-methyloxetane, 2- 2-methacryloyloxymethyl-2-methyloxymethyl-2-methyloxetane, 2-methacryloyloxymethyl-2- (2-methacryloyloxyethyl) oxetane, 2- (2-methacryloyloxyethyl) -2-methyloctane, 2- (Meta) acrylic compounds containing an oxetanyl group such as cetane, 2- (2-methacryloyloxyethyl) -2-ethyloxetane and 2- (2-methacryloyloxyethyl) And the like.

Among these monomers, glycidyl methacrylate, 2-methylglycidyl methacrylate, methacrylic acid-3,4-epoxycyclohexyl, methacrylic acid-3,4-epoxycyclohexylmethyl, 3- Methacryloyloxymethyl) -3-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, in view of the copolymerization reactivity with other monomers and the developability of the positive radiation-sensitive composition desirable.

The content of the epoxy group-containing structural unit (II) in the polymer [A] is not particularly limited as long as the desired heat resistance of the display interlayer insulating film is exhibited, and the content of the structural unit (I) and the epoxy group- When the unit (II) is contained, it is preferably 10 mass% or more and 60 mass% or less, more preferably 15 mass% or more and 55 mass% or less, based on the total structural units contained in the polymer [A] , And particularly preferably 20 mass% or more and 50 mass% or less.

On the other hand, in the case where one polymer molecule has a structural unit (I) and the other polymer molecule contains an epoxy group-containing structural unit (II), the total structure contained in another polymer molecule containing an epoxy group- The content of the epoxy group-containing structural unit (II) in the unit is preferably 20 mass% or more and 80 mass% or less, more preferably 30 mass% or more and 70 mass% or less, more preferably 35 mass% or more and 65 mass% Or less is particularly preferable.

[Other structural units]

The polymer [A] may contain other structural units other than the structural unit (I) and the structural unit (II) within the range not impairing the effect of the present invention.

Examples of the monomer giving another structural unit include a carboxyl group or a derivative thereof, and a monomer having a hydroxyl group.

Examples of the monomer having the carboxyl group or derivative thereof include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, 2-acryloyloxyethyl hexa Monocarboxylic acids such as hydrophthalic acid and 2-methacryloyloxyethylhexahydrophthalic acid; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; And the acid anhydrides of the above-mentioned dicarboxylic acids.

Examples of the monomer having a hydroxyl group include acrylic acid-2-hydroxyethyl ester, acrylic acid-3-hydroxypropyl ester, acrylic acid-4-hydroxybutyl ester, and acrylic acid-4-hydroxymethylcyclohexylmethyl ester Acrylic acid hydroxyalkyl esters; 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, methacrylic acid-5-hydroxypentyl ester, methacrylic acid- Hydroxyethyl methacrylate, hydroxyhexyl ester, methacrylic acid-4-hydroxymethyl-cyclohexylmethyl ester, and the like.

Among these monomers having a hydroxyl group, from the viewpoint of the copolymerization reactivity with other monomers and the heat resistance of the obtained interlayer insulating film for a display element, it is preferable to use acrylic acid-2-hydroxyethyl ester, acrylic acid-3-hydroxypropyl ester, Hydroxybutyl ester, methacrylic acid-2-hydroxyethyl ester, methacrylic acid-4-hydroxybutyl ester, acrylic acid-4-hydroxymethyl-cyclohexylmethyl ester, methacrylic acid-4-hydroxymethyl-cyclo Hexyl methyl esters are preferred.

As other monomers, for example,

Acrylic acid alkyl esters such as methyl acrylate and i-propyl acrylate;

Methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, and t-butyl methacrylate;

Acrylic acid-tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, acrylic acid -2- (tricyclo [5.2.1.0 ^2,6 ] decan-8- yloxy Acrylic acid alicyclic alkyl esters such as ethyl and isobornyl acrylate;

2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 2- (tricyclo [5.2.1.0 ^{2, 6} ] decan-8-yloxy) ethyl methacrylate, isobornyl methacrylate and the like;

Aryl esters of acrylic acid such as phenyl acrylate and benzyl acrylate, and aralkyl esters of acrylic acid;

Aralkyl esters of methacrylic acid and aryl esters of methacrylic acid such as phenyl methacrylate and benzyl methacrylate;

Dicarboxylic acid dialkyl esters such as diethyl maleate, diethyl fumarate and diethyl itaconate;

Unsaturated complex 5-membered cyclic methacrylate esters containing one oxygen atom such as tetrahydrofuranyl methacrylate, tetrahydrofurfuryl methacrylate, tetrahydrofuryl methacrylate, and tetrahydropyran-2-methyl methacrylate, and unsaturated complex 6-membered methacrylic acid esters ;

4-methacryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methacryloyloxymethyl- , 4-methacryloyloxymethyl-2-cyclohexyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl- 2-methyl-2-methyl-2-isobutyl-1,3-dioxolane, and the like; unsaturated heterocyclic 5-membered cyclic methacrylate esters containing two oxygen atoms such as methacryloyloxymethyl-

4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-acryloyloxymethyl-2,2-dimethyl- 4-acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-acryloyloxy Methyl-2-cyclopentyl-1,3-dioxolane, 4-acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane, 4- acryloyloxyethyl- Ethyl-1,3-dioxolane, 4-acryloyloxypropyl-2-methyl-2-ethyl- Unsaturated heterocyclic 5-membered ring acrylate esters containing two oxygen atoms such as 1,3-dioxolane;

Vinyl aromatic compounds such as styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and 4-isopropenylphenol;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Maleimide caproate, N-succinimidyl-3-maleimide propionate, N- (9-acridinyl) maleimide;

Conjugated diene-based compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene;

And other unsaturated compounds such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, and vinyl acetate.

Among these monomers, styrene, 4-isopropenylphenol, methacrylic tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, methacrylic acid tetrahydrofurfuryl, 1,3-butadiene, 4- Acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, N-cyclohexylmaleimide, N-phenylmaleimide and benzyl methacrylate, with monomers having the above- From the viewpoint of copolymerization reactivity and developability of the positive-tone radiation-sensitive composition.

The polystyrene-reduced weight average molecular weight (Mw) of the polymer [A] by gel permeation chromatography (GPC) is preferably 2.0 x 10 ^{3 to} 1.0 x 10 ⁵ , more preferably 5.0 x 10 ^{3 to} 5.0 x 10 ⁴ to be. By setting the Mw of the polymer [A] within the above-specified range, the sensitivity and alkali developability of the positive radiation sensitive composition can be increased.

The polystyrene reduced number average molecular weight (Mn) of the polymer [A] by GPC is preferably 2.0 x 10 ^{3 to} 1.0 x 10 ⁵ , more preferably 5.0 x 10 ^{3 to} 5.0 x 10 ⁴ . By setting the Mn of the polymer [A] within the above-specified range, the curing reactivity at the time of curing the coating film of the positive radiation-sensitive composition can be improved.

The molecular weight distribution (Mw / Mn) of the polymer [A] is preferably 3.0 or less, more preferably 2.6 or less. By setting the Mw / Mn of the polymer [A] to 3.0 or less, the developability of the obtained interlayer insulating film for a display element can be enhanced. The positive-tone radiation-sensitive composition containing the polymer [A] can easily form a desired pattern shape without developing residuals during development.

Mw and Mn of the present specification were measured by GPC under the following conditions.

Apparatus: GPC-101 (manufactured by Showa Denko Co., Ltd.)

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

Mobile phase: tetrahydrofuran

 Column temperature: 40 DEG C

Flow rate: 1.0 mL / min

Sample concentration: 1.0 mass%

Sample injection amount: 100 μL

Detector: differential refractometer

Standard material: monodisperse polystyrene

<Method of synthesizing [A] polymer>

The polymer [A] can be synthesized by radical copolymerization of the monomers imparting the respective structural units. For example, in the case of synthesizing the polymer [A] containing both the structural unit (I) and the epoxy group-containing structural unit (II) in the same polymer molecule, it is preferable to use a monomer having a structural unit (I) Lt; RTI ID = 0.0 &gt; (II). &Lt; / RTI &gt; On the other hand, when a polymer [A] having a structural unit (I) in one polymer molecule and an epoxy group-containing structural unit (II) in a different polymer molecule is synthesized, Radical polymerization of a polymerizable solution containing a monomer to obtain a polymer molecule having a structural unit (I), and radical polymerization of a polymerizable solution containing a monomer giving an epoxy group-containing structural unit (II) separately to obtain an epoxy group- (II) is obtained, and finally the two are mixed to obtain a polymer [A].

Examples of the solvent used in the polymerization reaction of the polymer [A] include the solvents exemplified in the following section of the preparation of the composition of the present invention.

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

In the polymerization reaction of the polymer [A], a molecular weight regulator may be used to adjust the molecular weight. Examples of the molecular weight regulator include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and thioglycolic acid; Azetidine derivatives such as dimethylzantogen sulfide and diisopropylzantogen disulfide; Terpinolene, alpha -methylstyrene dimer, and the like.

<[B] Arrhythmia>

[B] An acidogenic organism is a compound which generates an acid by the irradiation of radiation or by the application of heat. As the radiation, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like can be used. The positive-tone radiation-sensitive composition contains a polymer [A] having an acid-cleavable group and a [B] acid-generating organism, so that the positive-tone radiation-sensitive composition can exhibit a positive radiation-sensitive property. [B] The form of the scattered organism in the positive-tone radiation-sensitive composition of the present invention is not particularly limited as long as the form of the compound to be described later (hereinafter appropriately referred to as "[B] acid generator" Either a form of the acid generator injected as a part or a form of both of them may be used. Whether the acid is generated from the living body by irradiation of radiation or by application of heat can be determined by adjusting the temperature at the time of prebaking before exposure, the irradiation amount of radiation, the temperature at postbaking, etc., As the living body, it is preferable that an acid is generated by irradiation of radiation at the time of exposure, and an acid is generated by heat at the time of post-baking. By using these [B] acidogenic organics, not only the positive radiation-sensitive composition can exhibit positive radiation-sensitive properties, but also the [C] nitrogen-containing compound is deprotected during post-baking to perform the crosslinking reaction of the epoxy group It can be sufficiently advanced.

Examples of the acid generator [B] include an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a sulfonic acid compound, a sulfonic acid ester compound and a quinone diazide compound. These [B] acid generators may be used alone or in combination of two or more.

[Oxime sulfonate compound]

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

In the above formula (4), R ^B1 is a linear or branched alkyl group, cycloalkyl group, or aryl group. However, these groups may be substituted with some or all of the hydrogen atoms.

The linear or branched alkyl group represented by R ^B1 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The linear or branched alkyl group having 1 to 10 carbon atoms may be substituted, and examples of the substituent include a caproic ring group such as an alkoxy group having 1 to 10 carbon atoms and a 7,7-dimethyl-2-oxononorbornyl group And the like. The preferable alicyclic group is a bicycloalkyl group. The aryl group represented by R ^B1 is preferably an aryl group having 6 to 11 carbon atoms, more preferably a phenyl group or a naphthyl group. The aryl group may be substituted, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

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

In the formula (5), R ^B1 has the same meaning as in the formula (4). X is an alkyl group, an alkoxy group, or a halogen atom. m is an integer of 0 to 3; Provided that when plural Xs are present, plural Xs may be the same or different.

The alkyl group which may be represented by X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group represented by X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom represented by X is preferably a chlorine atom or a fluorine atom. As m, 0 or 1 is preferable. In the above formula (5), a compound wherein m is 1, X is a methyl group, and X is an ortho substituted position is preferable.

Examples of the oxime sulfonate compound represented by the formula (5) include compounds represented by the following formulas (5-1) to (5-5), and the like.

The compound (5-1) (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile, the compound (5-2) (5-octylsulfonyloxyimino- 5-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile, Compound 5-3 (camphorsulfonyloxyimino- , (5-4) (5- p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile and the compound (5-5) (5-octylsulfonyloxy Amino) - (4-methoxyphenyl) acetonitrile is available as a commercial product.

[Onium salts]

Examples of the onium salts include diphenyl iodonium salts, triphenylsulfonium salts, sulfonium salts, benzothiazonium salts, and tetrahydrothiophenium salts.

Examples of the diphenyl iodonium salt include diphenyl iodonium tetrafluoroborate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroarsenate, diphenyl iodonium tri Diphenyl iodonium trifluoroacetate, diphenyl iodonium-p-toluene sulfonate, diphenyl iodonium butyl tris (2,6-difluorophenyl) borate, 4- Bis (4-t-butylphenyl) iodonium hexafluoroarsenate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium-p- (4-t-butylphenyl) iodonium camphorsulfonic acid, and the like.

Examples of the triphenylsulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium- p-toluenesulfonate, triphenylsulfonium butyltris (2,6-difluorophenyl) borate, and the like.

Examples of the sulfonium salt include an alkylsulfonium salt, a benzylsulfonium salt, a dibenzylsulfonium salt, and a substituted benzylsulfonium salt.

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

Examples of the benzylsulfonium salt include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexa 4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro- 4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, and the like.

Examples of dibenzylsulfonium salts include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium Dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3- Methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate and the like.

Examples of the substituted benzylsulfonium salt include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p -Chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl- Hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and the like.

Examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p- 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, and the like can be used. .

Examples of the tetrahydrothiophenium salt include 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen- 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- 1- (4-n-butoxy) -1,2,2-tetrafluoro-2- (norbornan- (5-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethane (6-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) - (4-n-butoxynaphthalen-1-yl) tetrahydrothiophene- 1,1,2,2-tetrafluoroethanesulfonate, and the like.

[Sulfonimide compound]

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

[Quinone diazide compound]

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

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

Examples of the trihydroxybenzophenone include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, and the like. Examples of the tetrahydroxybenzophenone include 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'- Tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, and 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone. have. Examples of the pentahydroxybenzophenone include 2,3,4,2 ', 6'-pentahydroxybenzophenone and the like. Examples of the hexahydroxybenzophenone include 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone Phenone, and the like. Examples of the (polyhydroxyphenyl) alkane include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris -Tris (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, - [1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] Ethylidene] bisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'- tetramethyl-1,1'-spirobindene- , 6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavone and the like. Hydroxyphenyl) -7-hydroxychroman, 1- [1- (3- (4-hydroxyphenyl) Methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) ) -1- methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl) benzene, 4,6-bis {1- (4-hydroxyphenyl) - dihydroxybenzene.

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

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

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

In the condensation reaction of a phenolic compound or an alcoholic compound (mother nucleus) with 1,2-naphthoquinonediazidesulfonic acid halide, the amount of the phenolic compound or the alcoholic compound is preferably 30 mol% to 85 mol %, More preferably from 50 mol% to 70 mol% of 1,2-naphthoquinonediazidesulfonic acid halide. The condensation reaction can be carried out by a known method.

Examples of the quinone diazide compound include 1,2-naphthoquinone diazidesulfonic acid amides in which the ester bond of the mother nucleus is changed to an amide bond as described above, for example, 2,3,4-triaminobenzophenone 1,2 -Naphthoquinonediazide-4-sulfonic acid amide and the like are also suitably used.

As the acid generator [B], oxime sulfonate compounds and onium salts are preferable from the viewpoint of sensitivity and solubility. The oxime sulfonate compound is preferably the compound represented by the formula (4), more preferably the compound represented by the formula (5), and the compounds represented by the formulas (5-1) to (5-5) Are particularly preferred. As the onium salts, tetrahydrothiophenium salts and benzylsulfonium salts are preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, benzyl-4-hydroxy Phenylmethylsulfonium hexafluorophosphate is more preferable.

The content of the [B] acidogenic organism in the composition is preferably from 1 part by mass to 20 parts by mass, more preferably from 1 part by mass to 20 parts by mass, relative to 100 parts by mass of the polymer [A] More preferably 1 part by mass to 10 parts by mass. [B] By setting the content of the acidogenic organic matter to the above-specified range, the difference in solubility between the irradiated portion and the unirradiated portion of the irradiated portion of the aqueous alkaline solution becomes large and the patterning performance becomes good, The heat resistance of the substrate is also improved.

&Lt; [C] Nitrogen-containing compound &gt;

The [C] nitrogen-containing compound is an amine which is not deprotected by an acid generated from a [B] acidogenic organism at the time of exposure and is deprotected by the heat during postbaking and by the action of the acid generated from the acidogenic organism by this heat / RTI &gt; By deprotecting the [C] nitrogen-containing compound during post-baking, the reactivity as an amine compound is exerted and the cross-linking reaction of the epoxy group proceeds sufficiently. As a result, an interlayer insulating film for a display element having excellent surface hardness and heat resistance is formed can do.

[C] The nitrogen-containing compound is at least one nitrogen-containing compound selected from the group consisting of the nitrogen-containing compound (I) represented by the formula (2) and the nitrogen-containing compound (II) represented by the formula (3). Hereinafter, each compound will be described in detail.

[Nitrogen-containing compound (I)]

In the formula (2), R ⁴ and R ⁵ are each independently a hydrogen atom, an amino group, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. The alkyl group and the aryl group may include a hydroxyl group, a carboxyl group, a carbonyl group, an ester group, a sulfone group, an amide group, an ether group, a thiol group, a thioether group, an amino group or an amidino group. R ⁶ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Provided that R &lt; ⁴ &gt; and R &lt; ⁵ &gt; are connected to form a ring structure together with the nitrogen atom bonded to each other.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁴ , R ⁵ and R ⁶ include methyl, ethyl, n-propyl, n-butyl, n-pentyl, , a straight chain alkyl group such as an n-dodecyl group, an n-tetradecyl group and an n-octadecyl group, an i-propyl group, an i-butyl group, a tert- And a branched alkyl group such as an acyl group and a 3-hexyl group. Examples of the cycloalkyl group having ⁴ to 20 carbon atoms represented by R ⁶ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a 1-methylcyclopentyl group, Ethylcyclohexyl group, 1-ethylcyclohexyl group, 2-methyl-2-norbornyl group and 2-ethyl-2-norbornyl group. The aryl group having ⁶ to 20 carbon atoms represented by R ⁴ , R ⁵ and R ⁶ may be a monocyclic ring, a monocyclic ring or a condensed ring, and examples thereof include a phenyl group and a naphthyl group have. As R ^{6, in view} of the ability to control the reactivity of the [C] nitrogen-containing compound, the protecting function against the acid, and the ability to deprotect, the tertiary butyl group, tert-amyl group, 1-methylcyclohexyl group, Practical skill is preferable.

Examples of the nitrogen-containing compound (I) include N- (tert-butoxycarbonyl) -L-alanine, N- (tert-butoxycarbonyl) -L- ) - 2- (tert-butoxycarbonylamino) -3-cyclohexyl-1-propanol, (R) - (R) - (+) - 2- (tert-butoxycarbonylamino) -3-phenyl-1-propanol, (R) - (+) - 2- (tert-butoxycarbonylamino) -3-phenyl-2-propanol, Propanol, (R) - (+) - 2- (tert-butoxycarbonylamino) (Tert-butoxycarbonyl) -L-aspartic acid 4-benzyl ester, N- (tert-butoxycarbonyl) -O-benzyl-L-threonine, (S) - (-) - 1- (tert-butoxycarbonyl) -2-tert-butyl- Carbonyl) -2-tert-butyl-3-methyl-4-imidazoli (Tert-butoxycarbonyl) -3-cyclohexyl-L-alanine-methyl ester, N- (tert-butoxycarbonyl) -L-cysteine- N- (1-methylcyclohexylcarbonyl) ethanolamine, N- (1-ethylcyclohexylcarbonyl) ethanolamine, N- (tert-butoxycarbonyl) -L-glutamine, 1- (tert-butoxycarbonyl) -D-glucosamine, N- N- (tert-butoxycarbonyl) -L- isoleucine, N- (tert-butoxycarbonyl) -L-isoleucine- N- (tert-butoxycarbonyl) -L-lysine, N- (tert-butoxycarbonyl) -L-methionine, N- (Tert-butoxycarbonyl) -L-phenylalanine methyl ester, N- (tert-butoxycarbonyl) -L-phenylalanine, N- D-proline, N- (tert-butoxy) N- (tert-butoxycarbonyl) -L-proline-N'-methoxy-N'-methylamide, N- (S) - (-) - 1- (tert-amyloxycarbonyl) -2-pyrrolidinone Pyrrolidinemethanol, (S) - (-) - l- (1-ethyl-2-pyrrolidinecarbonyl) Pyrrolidine methanol, (R) - (+) - 1- (tert-butoxycarbonyl) -2-pyrrolidinemethanol and 1- (tert-butoxycarbonyl) L-serine, N- (tert-butoxycarbonyl) -L-serine-methyl ester , N- (tert-butoxycarbonyl) -L-threonine, N- (tert-butoxycarbonyl) -p-toluenesulfonamide, N- - Cysteine, N- (tert-butoxycarbonyl) -L-tryptophan, N- (tert-butoxycarbonyl) -L- tyrosine, N- Ester, N- (tert-butoxycarbonyl) -L-val , N- (tert-butoxycarbonyl) -L-valine-methyl ester, N- (tert-butoxycarbonyl) -L- valinol, tert- butylcarbamate, tert- butylcarbazate, butyl N- (3-hydroxypropyl) carbamate, tert-butyl N- (6-aminohexyl) carbamate, tert- butyl N- (benzyloxy) carbamate, , 3-dihydrooxazoline carboxylate, t-amyl 2-oxo-2,3-dihydrooxazoline carboxylate, 1-methylcyclohexyl 2-oxo-2,3-dihydrooxazoline carboxylate, 1- 2-oxo-2,3-dihydrooxazoline carboxylate, tert-butyl (1S, 4S) - (S) - (-) - 4-formyl-2, 3-dihydroxypropyl) carbamate, tert- 2-dimethyl-3-oxazolidinecarboxylate, tert-butyl [R- (R *, S *)] Butyl-1-pyrrolidinecarboxylate, tert-butyl N-methylcarbamate, tert-butyl N-methylcarbamate, (Tetrahydro-2-oxo-3-furanyl) carbamate.

Of these, N- (tert-butoxycarbonyl) -L-alanine methyl ester, (S) - (-) - 2- (tert- (R) - (+) - 2- (tert-butoxycarbonylamino) -3-phenyl- Propanol, (S) - (-) - 2- (tert-butoxycarbonylamino) -3-phenylpropanol, (R) - (+) - 2- Propanol, (S) - (-) - 2- (tert-butoxycarbonylamino) -3-phenyl-1-propanol, (S) - (-) - 2- (tert-butoxycarbonylamino) -1-propanol, (S) - (-) - 1- (tert-butoxycarbonyl) -2-tert-butyl-3-methyl-4-imidazole N- (tert-butoxycarbonyl) -3-cyclohexyl-L-alanine methyl ester, N- (tert-butoxycarbonyl) -L-cysteine methyl ester, N- N-propyl) ethanolamine, N- (tert-amyloxy 1- (tert-butoxycarbonyl) imidazole, N- (1-methylcyclohexylcarbonyl) ethanolamine, N- N-tert-butoxycarbonyl) -L-isoleucine, N- (tert-butoxycarbonyl) -L-isoleucine methyl ester, N- (tert-butoxycarbonyl) N- (tert-butoxycarbonyl) -L-proline N- (tert-butoxycarbonyl) -L-proline, N- (S) - (-) - 1- (tert-butoxycarbonyl) -2-pyrrolidine Methanol, (S) - (-) - 1- (tert-amylcarbonyl) -2-pyrrolidinemethanol, (R) - (+) - 1- (tert-butoxycarbonyl) (Tert-butoxycarbonyl) -S-trityl-L-cysteine, N- (tert-butoxycarbonyl) -L-tryptophane, N- (tert- -L-valine methyl ester, N- (tert-butoxycarbonyl) -L-valinol, tert-butyl N- (3-hydroxypropyl) carbamate, tert- Butyl (1S, 4S) - (-) - tert-butylcarbamate, tert-butyl N- (benzyloxy) Diazabicyclo [2.2.1] heptane-2-carboxylate, tert-butyl N- (2,3-dihydroxypropyl) carbamate, t- butyl 2-oxo-2,3-dihydro (S) - (-) - 4-formyl-2,2-dimethyl-3-oxazolidin e, (3-hydroxyphenyl) -1-methylethyl] carbamate, tert-butyl 4-oxo Butyl-1-pyrrolidinecarboxylate, tert-butyl (tetrahydro-2-oxo-3-furanyl) carbamate are preferable , The reactivity is controlled when the positive-tone radiation-sensitive composition is stored, and when the post-baking is performed, It is more preferably a nitrogen-containing compound represented by the in view, the following formula (2-1) to (2-7) to sufficiently proceed cross-linking reaction of the epoxy group.

The nitrogen-containing compound (I) may be used singly or in combination of two or more. Further, it may be used in combination with a basic compound described later, and the degree of crosslinking can be controlled by changing the addition ratio of the combination.

In the positive-tone radiation-sensitive composition, the content of the nitrogen-containing compound (I) is preferably 2 parts by mass to 30 parts by mass, more preferably 3 parts by mass to 20 parts by mass, per 100 parts by mass of the polymer [A]. By setting the content of the nitrogen-containing compound (I) within the above-specified range, the crosslinking reaction of the epoxy group is sufficiently promoted and side reactions with undesired epoxy groups are prevented by the excess amount, and the radiation sensitivity of the positive radiation- And lowering of the storage stability and deterioration of the transmittance and the voltage holding ratio of the resulting cured film can be prevented.

[Nitrogen-containing compound (II)]

The nitrogen-containing compound (II) has two carbamate structures in the molecule, as represented by the formula (3). In the above formula (3), R ⁷ and R ⁸ are each independently the same as R ⁴ above. R ⁹ and R ¹⁰ are each independently the same as R ⁶ above. A is an alkanediyl group having 1 to 12 carbon atoms or an arylene group having 6 to 20 carbon atoms.

The alkanediyl group having 1 to 12 carbon atoms represented by A includes, for example, methanediyl, ethanediyl, propanediyl, butanediyl, pentanediyl, and hexanediyl. As the arylene group having 6 to 20 carbon atoms represented by A, a divalent group obtained by removing two hydrogen atoms from an aryl group having ⁶ to 20 carbon atoms represented by R ⁴ , R ⁵ and R ⁶ in the formula (2) For example, phenylene group, naphthylene group and the like. Examples of R ⁹ and R ¹⁰ include tert-butyl group, tert-amyl group, 1-methylcyclohexyl group, 1-methylcyclohexyl group, and 1-methylcyclohexyl group, from the viewpoints of reactivity control ability, An ethylcyclohexyl group is preferred.

Examples of the nitrogen-containing compound (II) include compounds represented by the following formulas (3-1-1) to (3-1-9) and (3-2-1) to (3-2-4) .

In the nitrogen-containing compound (II), the reactivity is controlled when the positive-tone radiation-sensitive composition is stored, and from the viewpoint of satisfactorily deprotecting at the time of postbaking to sufficiently proceed the crosslinking reaction of the epoxy group, -1-3), (3-1-4), (3-1-5), (3-1-6) and (3-2-1).

In the positive-tone radiation-sensitive composition, the content of the nitrogen-containing compound (II) is preferably 2 parts by mass to 30 parts by mass, more preferably 3 parts by mass to 20 parts by mass, per 100 parts by mass of the polymer [A]. By setting the content of the nitrogen-containing compound (II) to the above-specified range, the crosslinking reaction of the epoxy group is sufficiently promoted and side reactions with undesired epoxy groups are prevented by the excess amount, and the radiation sensitivity of the positive radiation- And lowering of the storage stability and deterioration of the transmittance and the voltage holding ratio of the resulting cured film can be prevented.

When the nitrogen-containing compounds (I) and (II) are used in combination, it is preferable that the total amount of the nitrogen-containing compounds (I) and (II) is 2 parts by mass to 30 parts by mass with respect to 100 parts by mass of the polymer (A).

&Lt; [D] Surfactant &gt;

[D] The surfactant can further improve the film formability of the positive radiation-sensitive composition. Examples of the [D] surfactant include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surface-active agent. By containing the [D] surfactant in the positive-tone radiation-sensitive composition, the surface smoothness of the coating film can be improved, and the resulting film-thickness uniformity of the interlayer insulating film for a display element can be further improved. These surfactants may be used alone or in combination of two or more.

As the fluorine-based surfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least any of the terminal, main chain and side chain is preferable, and for example, 1,1,2,2-tetrafluoro-n-octyl Tetrafluoro-n-octyl (n-hexyl) ether, hexaethylene glycol di (1,1,2,2- Hexafluoro-n-pentyl) ether, octaethylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di (1,1,2,2,3- Hexafluoro-n-pentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, perfluoro-n-dodecane sulfonic acid Sodium, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,3,3,9,9,10,10-decafluoro-n-dodecane , Sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarbonate, diglycerin tetrakis (fluoroalkylpolyoxy Perfluoroalkylpolyoxyethanol, perfluoroalkylalkoxylate, carbonic acid fluoroalkyl ester, and the like can be used in combination with an organic peroxide such as methylene chloride, .

Examples of commercially available products of the fluorinated surfactants include BM-1000, BM-1100 (manufactured by BM CHEMIE), Megaface F142D, Copper F172, Copper F173, Copper F183, Copper F178, Copper F191, Copper F471, Fluorad FC-170C, FC-171, FC-430 and FC-431 (manufactured by Sumitomo 3M Ltd.), Surflon (manufactured by Dainippon Ink and Chemicals, Incorporated) S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103 and SC-104 SC-105, SC-106 (manufactured by Asahi Glass), Eftop EF301, EF303, EF352 (manufactured by Shin Akitakase), Ftergent FT-100, 110, FT-140A, FT-150, FT-250, FT-251, Copper FT-300, Copper FT-310, Copper FT-400S, Copper FTX-218, Copper FT- And the like.

Examples of commercially available silicone surfactants include Toray silicone DC3PA, Copper DC7PA, Copper SH11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA, Copper SH-190, Copper SH-193, Copper SZ-6032 TSF-4440, TSF-4446, TSF-4460, TSF-4440, TSF-4440, TSF-4440, and TSF-4460 FLUID (manufactured by Toray Dow Corning Silicone) -4452 (manufactured by GE Toshiba Silicone), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; Polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; (Meth) acrylic acid-based copolymer. Examples of commercially available nonionic surfactants include Polyflow No. 57 and 95 (manufactured by Kyowa Chemical Co., Ltd.).

The content of the [D] surfactant in the positive-tone radiation-sensitive composition is preferably 0.05 parts by mass or more and 5 parts by mass or less, more preferably 0.1 parts by mass or more, per 100 parts by mass of the polymer [A] 2 parts by mass or less. By setting the content of the [D] surfactant within the above-specified range, it is possible to suppress film roughening when a coating film is formed on a substrate.

<[E] Adhesion preparation>

In the positive-tone radiation-sensitive composition, in order to improve the adhesion between an inorganic substance serving as a substrate such as a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, copper, or aluminum, ] Adhesion aid can be used. As such an adhesion aid, a functional silane coupling agent is preferably used. Examples of the functional silane coupling agent include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group (preferably an oxiranyl group), and a thiol group.

Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane,? - Glycidoxypropyltrimethoxysilane, gamma -glycidoxypropylalkyldialkoxysilane,? -Chloropropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyl tri Methoxysilane and the like. Of these,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropylalkyldialkoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? -Methacryloxypropyltrimethoxysilane Lt; / RTI &gt; is preferred.

The content of the [E] adhesion aid in the positive-tone radiation-sensitive composition is preferably 0.5 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass or more, based on 100 parts by mass of the polymer [A] Parts by mass or less. [E] By setting the amount of the adhesion aid to the above specific range, adhesion between the display element interlayer insulating film and the substrate is improved.

&Lt; Other optional components &gt;

In addition to the above components [A] to [E], the positive-tone radiation-sensitive composition may contain other optional components such as a basic compound, if necessary, without impairing the effects of the present invention.

[Basic compound]

Since the positive-tone radiation-sensitive composition contains a basic compound, the diffusion length of the acid generated from the [B] acidogenic organism can be appropriately controlled by exposure, and the pattern developing property can be improved. The basic compound may be selected from those used as a chemically amplified resist, and examples thereof include aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, and quaternary ammonium carbonic acid salts.

Examples of the aliphatic amine include aliphatic amines such as ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, Such as cyclopentylamine, cyclohexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine, dimethylamine, diethylamine, di di-n-propylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptyl And examples thereof include aliphatic amines such as amine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, , Triethylamine, tri-n-propylamine, triisopropylamine , Tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, N, N ', N'-tetramethylmethylenediamine, N, N, N', N'-tetramethylethylenediamine, N'-tetramethyltetraethylenepentamine, and the like.

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

Examples of the aromatic amines and heterocyclic amines include aniline, N-methylaniline, N-ethyl aniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, Nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N, N-diethylaniline, Aniline derivatives such as N-dimethyltoluidine; Diphenylamine, diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene; Pyrrole derivatives such as pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole and N-methylpyrrole; Oxazole derivatives such as oxazole and isoxazole; Thiazole derivatives such as thiazole and isothiazole; Imidazole derivatives such as imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole and triphenylimidazole; Pyrazole derivatives, &lt; / RTI &gt; Pyrroline derivatives such as pyrroline and 2-methyl-1-pyrroline; Pyrrolidine derivatives such as pyrrolidine, N-methylpyrrolidine, pyrrolidinone, and N-methylpyrrolidone; Imidazolidine derivatives, pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3- Methyl-4-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl- Pyridine derivatives such as 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine and nicotine; Pyrazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazole derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives; Morpholine derivatives such as morpholine and 4-methylmorpholine; Indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives; Quinoline derivatives such as quinoline, 3-quinolinecarbonitrile and 8-oxyquinoline; A quinoxaline derivative, a quinoxaline derivative, a phthalazine derivative, a purine derivative, a pyridine derivative, a carbazole derivative, a phenanthridine derivative, an acridine derivative, a phenazine derivative, an isoquinoline derivative, a cinnoline derivative, Dianhydrides, adenine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [ And cyclic amines such as cyclo [5.3.0] -7-undecene.

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

Further, basic compounds represented by the following formulas (6) and (7) and the like can be given.

In the formulas (6) and (7), R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁷ and R ⁴⁸ each independently represent a straight chain, branched chain or cyclic alkylene group having 1 to 20 carbon atoms. R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁹ and R ⁵⁰ are each a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Provided that some or all of the hydrogen atoms of 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 each other to form a ring structure. S, T, and U are each independently an integer of 0 to 20. When S, T and U are all 0, R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁹ and R ⁵⁰ are not all hydrogen atoms.

The number of carbon atoms of the alkylene group represented by R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁷ and R ⁴⁸ is 1 to 20, preferably 1 to 10, and more preferably 1 to 8. Specific examples thereof include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, an n-pentylene group, an isopentylene group, a hexylene group, a nonylene group, And a cyclohexylene group.

The number of carbon atoms of the alkyl group represented by R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁹ and R ⁵⁰ is 1 to 20, preferably 1 to 8, more preferably 1 to 6. These may be linear, branched or cyclic. Specific examples thereof include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, An acyl group, a tridecyl group, a cyclopentyl group, and a cyclohexyl group.

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 cyclic structure, the number of carbon atoms is typically 1 to 20, Preferably 1 to 8, and more preferably 1 to 6. These ring structures may have branched alkyl groups of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. S, T, and U are preferably an integer of 1 to 10, and more preferably an integer of 1 to 8.

Examples of the basic compound represented by the above formulas (6) and (7) include tris {2- (methoxymethoxy) ethyl} amine, tris {2- (methoxyethoxy) ethyl} amine, tris [2- (2-methoxyethoxy) ethyl} amine, tris {2- (2-methoxyethoxy) ethyl} Ethyl} amine, tris [2- (1-ethoxyethoxy) ethyl] amine, tris {2- 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- -18-crown-6, and the like.

Examples of the basic compound include tertiary amines, aniline derivatives, pyrrolidine derivatives, pyridine derivatives, quinoline derivatives, amino acid derivatives, tris {2- (methoxymethoxy) ethyl} amine, tris { Ethoxy) ethyl} amine, tris [2 - {(2-methoxyethoxy) methyl} ethyl] amine and 1-aza-15-crown-5.

The content of the basic compound in the positive-tone radiation-sensitive composition is preferably 0.001 part by mass to 1 part by mass, more preferably 0.005 part by mass to 0.2 part by mass, relative to 100 parts by mass of the polymer [A]. By setting the content of the basic compound within the above-specified range, the pattern developability is further improved.

&Lt; Process for preparing positive-tone radiation-sensitive composition &gt;

The positive-tone radiation-sensitive composition is prepared by dissolving or dispersing the [A] polymer, the [B] acidogenic organopolysiloxane, the [C] nitrogen-containing compound as a suitable component, and other optional components, do. For example, the positive radiation-sensitive composition can be prepared by mixing the components in a predetermined ratio in a solvent.

As the solvent, those in which each component is uniformly dissolved or dispersed and do not react with each component are suitably used. Examples of the solvent include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionate , Aromatic hydrocarbons, ketones, and other esters. These solvents may be used alone or in combination of two or more.

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

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

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

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

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

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

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

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

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

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

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

Among these solvents, from the viewpoints of excellent solubility or dispersibility, non-reactivity with each component, and easiness of forming a film, it is preferable to use an ether such as a dialkyl ether, a diethylene glycol alkyl ether, an ethylene glycol alkyl ether acetate Propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, ketones and esters are preferable, and in particular, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, methyl cellosolve acetate, ethyl cellosolve, Propyleneglycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate , Methyl 2-hydroxy-2-methylpropionate, 2- Methyl propionate, ethyl lactate, methyl lactate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 2-methoxypropionate and ethyl 2-methoxypropionate are preferable, and diisopropyl ether, Di-n-pentyl ether, diisopentyl ether and di-n-hexyl ether are more preferable, and diisopentyl ether is particularly preferable. By using such a solvent, when the radiation sensitive composition is applied to a large glass substrate by a slit coating method, it is possible not only to shorten the drying process time but also to further improve the coating property (suppress coating unevenness).

Further, in addition to the above-mentioned solvent, if necessary, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetonyl acetone, isophorone, Benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, And a high boiling solvent such as carbitol acetate may be used in combination.

When the positive radiation-sensitive composition is prepared in the form of a solution or a dispersion, the proportion of the components other than the solvent in the solution can be set arbitrarily depending on the purpose of use and the desired film thickness, but is preferably 5 mass% to 50 mass %, More preferably 10% by mass to 40% by mass, and particularly preferably 15% by mass to 35% by mass.

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

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

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

(1) a step of forming a coating film of the positive radiation-sensitive composition on a substrate,

(2) a step of irradiating at least a part of the coating film with radiation,

(3) a step of developing the coating film irradiated with the radiation, and

(4) heating the developed coating film.

By the forming method of the present invention using the positive-tone radiation-sensitive composition, an interlayer insulating film for a display element which is excellent in surface hardness and heat resistance and sufficiently satisfactory in transmittance and voltage holding ratio can be formed. Hereinafter, each process will be described in detail.

[Step (1)]

In the present step, the solution or dispersion of the positive-tone radiation-sensitive composition is applied onto the substrate, and then the coated surface is preferably pre-baked to remove the solvent to form a coated film. Examples of the application method include a spray method, a roll coating method, a rotary coating method (spin coating method), a slit die coating method, and a bar coating method. Of these, the spin coating method and the slit die coating method are preferable, and the slit die coating method is more preferable.

Examples of the substrate include glass, quartz, silicon, resin, and the like. Examples of the resin include ring-opening polymers of polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide and cyclic olefin, and hydrogenated products thereof. The conditions for prebaking vary depending on the kind of each component, blending ratio, etc., but can be set to about 70 to 120 캜 for about 1 to 10 minutes.

[Step (2)]

In this step, at least a part of the formed coating film is exposed to radiation. When exposure is performed, exposure is usually performed through a photomask having a predetermined pattern. As the radiation used for exposure, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation containing ultraviolet light of 365 nm is more preferable. The exposure dose is preferably 300 J / m 2 to 5,000 J / m 2, more preferably 400 J / m 2 to 1,500 J / m 2, as measured by a light meter (OAI model 356, manufactured by OAI Optical Associates) / M &lt; 2 &gt; is more preferable.

[Step (3)]

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

To the aqueous alkali solution, a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added in an appropriate amount. The concentration of the alkali in the aqueous alkali solution is preferably 0.1% by mass or more and 5% by mass or less from the viewpoint of achieving adequate developability. Examples of the developing method include a puddle method, a dipping method, a swing dipping method, a shower method, and the like. The developing time varies depending on the composition of the positive-tone radiation-sensitive composition and is, for example, about 10 seconds to 180 seconds. Following this development processing, for example, water washing is carried out for 30 seconds to 90 seconds, and then air is blown with compressed air or compressed nitrogen, for example, to form a desired pattern.

[Step (4)]

In this step, the developed coating film is heated. For heating, the patterned thin film is heated by using a heating apparatus such as a hot plate or an oven to accelerate the curing reaction of the [A] polymer and the [C] nitrogen-containing compound to obtain a cured product. The heating temperature is, for example, about 120 ° C to 250 ° C. The heating time varies depending on the type of the heating apparatus, for example, about 5 minutes to 30 minutes for a hot plate and 30 minutes to 90 minutes for an oven. Further, a step baking method in which two or more heating steps are performed may be used. In this manner, a patterned thin film corresponding to the target interlayer insulating film for a display element can be formed on the surface of the substrate. The use of the cured film is not limited to the interlayer insulating film for a display element, and can also be used as a spacer or a protective film.

The film thickness of the formed interlayer insulating film for a display element is preferably 0.1 mu m to 8 mu m, more preferably 0.1 mu m to 6 mu m, particularly preferably 0.1 mu m to 4 mu m.

Example

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

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

[Synthesis Example 1]

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed. 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 methylstyrene dimer were added and the mixture was purged with nitrogen, and stirring was started gently. The temperature of the solution was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-1). The Mw of the polymer (A-1) was 9,000. The solid concentration of the polymer solution was 32.1 mass%.

[Synthesis Example 2]

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed. Subsequently, 5 parts by mass of methacrylic acid, 40 parts by mass of 2-tetrahydropyranyl 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 methylstyrene dimer were added and the mixture was purged with nitrogen, and stirring was started gently. The temperature of the solution was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-2). The Mw of the polymer (A-2) was 9,000. The solid concentration of the polymer solution was 31.3% by mass.

[Synthesis Example 3]

7 parts by mass of 2,2'-azobis (methyl 2-methylpropionate) and 200 parts by mass of propylene glycol monomethyl ether acetate were placed in a flask equipped with a condenser and a stirrer. Subsequently, 67 parts by mass of 1-n-butoxyethyl methacrylate, 23 parts by mass of benzyl methacrylate and 10 parts by mass of methacrylic acid were purged with nitrogen, followed by gentle agitation. The temperature of the solution was raised to 80 캜, and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (a-1). The Mw of the polymer (a-1) was 9,000. The solid concentration of the polymer solution was 30.3 mass%.

[Synthesis Example 4]

7 parts by mass of 2,2'-azobis (methyl 2-methylpropionate) and 200 parts by mass of propylene glycol monomethyl ether acetate were placed in a flask equipped with a condenser and a stirrer. Subsequently, 90 parts by mass of 1-benzyloxyethyl methacrylate, 6 parts by mass of 2-hydroxyethyl methacrylate and 4 parts by mass of methacrylic acid were purged with nitrogen, followed by gentle agitation. The temperature of the solution was raised to 80 占 폚, and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (a-2). The Mw of the polymer (a-2) was 9,000. The solid content concentration of the polymer solution was 31.2 mass%.

[Synthesis Example 5]

7 parts by mass of 2,2'-azobis (methyl 2-methylpropionate) and 200 parts by mass of propylene glycol monomethyl ether acetate were placed in a flask equipped with a condenser and a stirrer. Subsequently, 85 parts by mass of 2-tetrahydropyranyl methacrylate, 7 parts by mass of 2-hydroxyethyl methacrylate and 8 parts by mass of methacrylic acid were charged and replaced with nitrogen, and stirring was gently started. The temperature of the solution was raised to 80 캜, and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (a-3). The Mw of the polymer (a-3) was 10,000. The solid concentration of the polymer solution was 29.2 mass%.

[Synthesis Example 6]

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed. Subsequently, 52 parts by mass of glycidyl methacrylate and 48 parts by mass of benzyl methacrylate were added and replaced with nitrogen, followed by gentle agitation. The temperature of the solution was raised to 80 캜, and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (aa-1). The Mw of the polymer (aa-1) was 10,000. The solid concentration of the polymer solution was 32.3 mass%.

[Synthesis Example 7]

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed. 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 replaced with nitrogen, followed by gentle agitation. The temperature of the solution was raised to 80 캜, and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (aa-2). The Mw of the polymer (aa-2) was 10,000. The solid content concentration of the polymer solution was 33.2 mass%.

[Synthesis Example 8]

7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed in a flask equipped with a condenser and a stirrer. Subsequently, 35 parts by mass of 1-n-butoxyethyl methacrylate, 35 parts by mass of benzyl methacrylate and 30 parts by mass of glycidyl methacrylate were purged with nitrogen and stirred gently. The temperature of the solution was raised to 80 캜, and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (aa-3). The Mw of the polymer (aa-3) was 10,000. The solid concentration of the polymer solution was 32.3 mass%.

<Preparation of positive-tone radiation-sensitive composition>

Hereinafter, the components used for preparing the positive radiation-sensitive compositions of the examples and the comparative examples will be described in detail.

[B] 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 Chiba Specialty Chemicals)

B-4: (5-Octylsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile (IRGACURE PAG 108 manufactured by Chiba Specialty Chemicals)

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

B-6: (camphorsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile (CGI1380 manufactured by Chiba Specialty Chemicals)

B-7: (5-Octylsulfonyloxyimino) - (4-methoxyphenyl) acetonitrile (CGI725 manufactured by Chiba Specialty Chemicals)

[C] Nitrogen-containing compound

C-1: The nitrogen-containing compound represented by the formula (2-1)

C-2: A nitrogen-containing compound represented by the formula (2-2)

C-3: A nitrogen-containing compound represented by the above formula (2-4)

C-4: A nitrogen-containing compound represented by the formula (3-1-3)

C-5: A nitrogen-containing compound represented by the formula (3-2-1)

[D] Surfactant

D-1: Silicone surfactant (manufactured by Toray Dow Corning Silicone, SH 8400 FLUID)

D-2: Fluorine-based surfactant (manufactured by NEOS, Fotogen FTX-218)

[E] Adhesion preparation

E-1:? -Glycidoxypropyltrimethoxysilane

E-2: Synthesis of? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane

E-3:? -Methacryloxypropyltrimethoxysilane

[Example 1]

, 3.0 parts by mass of (B-4) as the acid generator [B] in an amount of 100 parts by mass (solid content) of the solution (A- 5 parts by mass of (C-1) as a nitrogen-containing compound, (D-1) as a surfactant (D-1) and 3.0 parts by mass of (E- Mu] m membrane filter to prepare a positive radiation-sensitive composition.

[Examples 2 to 12 and Comparative Examples 1 and 2]

Each positive-tone radiation-sensitive composition was prepared in the same manner as in Example 1, except that the kinds and blending amounts of the respective components were changed as shown in Table 1. In Table 1, &quot; - &quot; indicates that the corresponding component is not used.

<Evaluation>

The following evaluations were carried out using each of the prepared positive-tone radiation-sensitive compositions. The results are shown in Table 1.

[Radiation sensitivity (J / m 2)]

Hexamethyldisilazane (HMDS) was applied onto a chromium-deposited glass of 550 x 650 mm and heated at 60 占 폚 for 1 minute. Each positive-tone radiation-sensitive composition was coated on the chromium-deposited glass after the HMDS treatment using a slit die coater (TR632105-CL, manufactured by Tokyo Ohka Kogyo Co., Ltd.), the solvent was removed under a vacuum set at an ultimate pressure of 100 Pa , And further baked at 90 DEG C for 2 minutes to form a coating film having a film thickness of 3.0 mu m. Subsequently, the coating film was irradiated with radiation with varying exposure dose through a mask having a pattern of 60 mu m line-and-space (10 to 1) using an exposure machine (manufactured by Canon, MPA-600FA). Then, it was developed with tetramethylammonium hydroxide aqueous solution of 0.4 mass% at 25 캜 for 80 seconds. Subsequently, the substrate was subjected to water washing with ultra-pure water for 1 minute, and then dried to form a pattern on the chromium-deposited glass substrate after the HMDS treatment. At this time, the radiation sensitivity (J / m 2) was determined as an exposure amount necessary for completely dissolving the 6 탆 space pattern. It was judged that the sensitivity was good when this value was 600 (J / m &lt; 2 &gt;) or less.

[Transmittance (%)]

A coating film was formed on the silicon substrate in the same manner as in the above evaluation of the radiation sensitivity. Without exposure, this silicon substrate was heated in a clean oven at 220 캜 for 1 hour to obtain a cured film. The transmittance (%) at a wavelength of 400 nm was measured and evaluated by using a spectrophotometer (150-20 type double beam, manufactured by Hitachi, Ltd.). When the transmittance was less than 90%, it was judged that the transparency was poor.

[Surface hardness]

The pencil hardness (surface hardness) of the cured film was measured by the pencil scratch test of JIS K-5400-1990 8.4.1 with respect to the substrate having the cured film formed by the evaluation of the transmittance. When the value is 3H or more, it is judged that the surface hardness of the display element interlayer insulating film is good, and it can be said that it has sufficient curability.

[Heat resistance (%)]

A coating film was formed on the silicon substrate by operating in the same manner as in the evaluation of the radiation sensitivity. Subsequently, the coating film was irradiated with radiation with varying exposure dose and exposure to 0.4% by mass of tetramethylammonium hydroxide aqueous solution with a mask having a line-and-space (one-to-one) pattern of 100 m Lt; RTI ID = 0.0 &gt; C &lt; / RTI &gt; The development time was 80 seconds. Subsequently, water washing with ultra-pure water for 1 minute was carried out, followed by drying to form a pattern. After development, the pattern height (T1) was measured by a stylus type film thickness measuring apparatus? -Step (manufactured by KLA Denk Co.). Thereafter, the patterned silicon substrate was heated in a clean oven at 220 캜 for one hour to obtain a pattern after heat curing. Thus, the pattern height t1 after heat curing was measured, and the heat shrinkage percentage (%) before and after the heat curing was calculated from the following equation, and this was regarded as heat resistance (%).

Heat resistance (%) = {(T1-t1) / T1} 100

It can be said that the larger the value of the heat resistance is, the more the crosslinking reaction proceeds. In addition, the heat shrinkage thus generated is a level that does not particularly affect the actual use.

[Voltage Conservation Rate (%)]

Each of the radiation-sensitive resin compositions was spin-coated on a soda glass substrate on which an SiO ₂ film was formed to prevent dissolution of sodium ions on the surface and an ITO (indium-tin oxide alloy) electrode was deposited in a predetermined shape , And then prebaked in a clean oven at 90 캜 for 10 minutes to form a coating film having a thickness of 2.0 탆. Subsequently, the coated film was exposed at an exposure amount of 500 J / m &lt; 2 &gt; without interposing a photomask. Thereafter, post-baking was performed at 230 캜 for 30 minutes to cure the coating film. Subsequently, the substrate on which the pixel was formed and the substrate on which the ITO electrode had been deposited in a predetermined shape were bonded to each other with a sealing material mixed with 0.8 mm glass beads, and then a liquid crystal cell MLC6608 was injected into the liquid crystal cell. The liquid crystal cell was placed in a thermostatic chamber at 60 占 폚 and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage preservation rate measuring system (Model VHR-1A, manufactured by Toyo Technica). The applied voltage at this time is a square wave of 5.5 V, and the measurement frequency is 60 Hz. The voltage holding ratio (%) is a value obtained from the following formula.

Voltage Conservation Rate (%) = (potential difference between the liquid crystal cell after 16.7 milliseconds / voltage applied at 0 milliseconds) × 100

When the voltage holding ratio of the liquid crystal cell is 90% or less, the liquid crystal cell can not maintain the applied voltage at a predetermined level for 16.7 milliseconds and can not sufficiently orient the liquid crystal. The "burn- There is a high possibility of causing it.

[Storage stability (%)]

Each of the radiation sensitive resin composition solutions was allowed to stand in an oven at 40 占 폚 for 1 week, and the viscosity before and after being placed in an oven was measured to determine the viscosity change rate (%). When the viscosity change rate was 5% or less, it was judged that the storage stability was good, and when it was more than 5%, it was judged that the storage stability was poor. The viscosity was measured at 25 캜 using an E-type viscometer (VISCONIC ELD.R, manufactured by Toray Industries, Inc.).

As is evident from the results in Table 1, the positive radiation-sensitive compositions of Examples 1 to 10 are superior in surface hardness to the radiation-sensitive compositions of Comparative Examples 1 and 2 which do not contain the [C] nitrogen- . It was also found that the crosslinking of the epoxy group was sufficiently proceeded from the value of the heat resistance. It has also been found that the positive radiation-sensitive compositions of these Examples can form an interlayer insulating film for a display device which not only has excellent storage stability and sufficient radiation sensitivity but also satisfies generally required characteristics such as transmittance and voltage holding ratio. Compared with Examples 1 to 10, the surface hardness was slightly lowered in Example 11, and in Example 12, the surface hardness was excellent, but the crosslinking reactivity was too high, The transmittance and the voltage holding ratio were slightly lowered. In view of the above, good results are obtained for all of the positive radiation-sensitive compositions of Examples 1 to 12, but the content of the [C] nitrogen-containing compound is preferably 2 parts by mass or more per 100 parts by mass of the polymer [A] It can be said that 30 parts by mass or less is preferable.

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

Claims (6)

[A] a polymer comprising a structural unit (I) having a group represented by the following formula (1) and an epoxy group-containing structural unit (II) in the same or different polymer molecules,
[B] Arrhythmia, and
[C] at least one nitrogen-containing compound selected from the group consisting of a nitrogen-containing compound (I) represented by the following formula (2) and a nitrogen-containing compound (II) represented by the following formula (3)
A positive radiation-sensitive composition comprising:

(In the formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, with the proviso that some or all of the hydrogen atoms of the alkyl group, cycloalkyl group, An alkoxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group or a haloalkyl group; and R ¹ and R ² may be the same or different and each represents a hydrogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group, is not ² when both a hydrogen atom; R ³ is an alkyl group, cycloalkyl group, aralkyl group, aryl group, or -M (R ^3m) group represented by _3; yi M is a Si, Ge or Sn; R ^3m R ¹ and R ³ may be connected to form a cyclic ether structure, provided that some or all of the hydrogen atoms of these groups represented by R ^{3 may} be replaced by a halogen atom, a hydroxyl group, a nitro group , A cyano group, a carboxyl group, a car Group, a cycloalkyl group, an aryl group, an alkoxy group, an acyl group, Good optionally substituted by an acyloxy group, alkoxycarbonyl group, or a haloalkyl group)

(Wherein R ⁴ and R ⁵ are each independently a hydrogen atom, an amino group, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, provided that the alkyl group and the aryl group each have a hydroxyl group, R ⁶ may be an alkyl group having 1 to 20 carbon atoms, an alkyl group having 4 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a carboxyl group, a carbonyl group, an ester group, a sulfone group, an amide group, an ether group, a thiol group, A cycloalkyl group having 6 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, provided that R ⁴ and R ⁵ may form a cyclic structure together with the nitrogen atom bonded to each other)

(In the formula (3), R ⁷ and R ⁸ are each independently the same as R ⁴ , R ⁹ and R ¹⁰ are each independently the same as R ⁶ , A is a C 1-12 An alkanediyl group having 6 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms). The method according to claim 1,
At least one group selected from the group consisting of R ⁶ in the formula (2) and R ⁹ and R ¹⁰ in the formula (3) is a tert-butyl group, a tert-amyl group, A cyclohexyl group or a 1-ethylcyclohexyl group. The method according to claim 1,
[C] The positive radiation-sensitive composition according to any one of claims 1 to 3, wherein the content of the nitrogen-containing compound is 2 parts by mass or more and 30 parts by mass or less based on 100 parts by mass of the polymer [A]. The method according to claim 1,
A positive radiation-sensitive composition for use in forming an interlayer insulating film for a display element. (1) a step of forming a coating film of the positive radiation-sensitive composition described in any one of claims 1 to 4 on a substrate,
(2) a step of irradiating at least a part of the coating film with radiation,
(3) a step of developing the coating film irradiated with the radiation, and
(4) a step of heating the developed coating film
Of the interlayer insulating film for a display element. An interlayer insulating film for a display element formed of the positive radiation sensitive composition according to any one of claims 1 to 4.