KR101762150B1 - Positive radiation-sensitive composition, interlayer insulating film and method for forming the same - Google Patents

Abstract

(Problem) A positive radiation-sensitive composition having excellent radiation sensitivity, having an excellent interlayer insulating film having high light transmittance and voltage holding ratio, and capable of coping with changes in cured film forming conditions, An interlayer insulating film formed from the composition, and a method of forming the interlayer insulating film.
(A) a polymer having a structural unit containing a group represented by the following formula (1) and an epoxy group-containing structural unit in the same or different polymer molecules, [B] a photoacid generator, and [C] Containing compound as a positive radiation-sensitive composition.

Description

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

The present invention relates to a positive-tone radiation-sensitive composition suitable as a material for forming an interlayer insulating film of a display element such as a liquid crystal display element (LCD) or an organic EL display element (OLED), an interlayer insulating film formed of the composition, 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 the interlayer insulating film obtained therefrom is required to have excellent heat resistance and the like.

In recent years, display devices such as liquid crystal display devices and organic EL display devices tend to be large-screen, high-brightness, high-definition, high-speed response, and thinner. For this reason, the radiation sensitive composition for forming an interlayer insulating film used in a display device of a display device is required to have high sensitivity to radiation, as well as to have a high voltage holding ratio and a high light transmittance, More excellent performance is required.

Acrylic resins are widely used as components of the positive radiation-sensitive composition corresponding to these various demands. For example, in Japanese Patent Application Laid-Open No. 2004-4669, a crosslinking agent, an acid generator and itself are dissolved in an aqueous alkali solution Characterized in that it contains a resin which is insoluble or hardly soluble but has a protecting group capable of dissociating by the action of an acid and becomes soluble in an aqueous alkali solution after the protecting group is cleared A positive chemical amplification resist composition has been proposed. Further, Japanese Patent Laid-Open No. 2004-264623 proposes a radiation-sensitive resin composition comprising a resin containing an acetal structure and / or a ketal structure and an epoxy group, and an acid generator.

However, when the above-described conventional radiation-sensitive resin composition is used to form an interlayer insulating film, for example, when the prebaking is performed at a relatively low temperature after coating, or when the development time is extended , The developability and, furthermore, the pattern formability may be lowered. That is, the conventional radiation-sensitive resin composition can not sufficiently cope with various changes in cured film forming conditions at an actual production site, and there is room for improvement in this respect.

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

The present invention has been made based on the above-described circumstances, and an object of the present invention is to provide an excellent interlayer insulating film having excellent radiation sensitivity and having excellent light transmittance and voltage holding ratio, A positive-ion radiation-sensitive composition having an antistatic property and a pattern-forming property, an interlayer insulating film formed from the composition, and a method for forming the interlayer insulating film.

According to an aspect of the present invention,

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

[B] the photoacid generator, and

[C] a compound represented by the following formula (2)

Based on the total weight of the composition.

(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, and when some or all of the hydrogen atoms of the alkyl group, cycloalkyl group or aryl group are substituted with a substituent good (where, R ¹ and R ² is no case that all are hydrogen atoms); R ³ is a group represented by the alkyl group, cycloalkyl group, aralkyl group, aryl group, or -M (R ^3m) ₃ (M is Si, Ge or Sn and R ^3m is an alkyl group), some or all of these hydrogen atoms may be substituted with a substituent, and R ¹ and R ³ may be connected to form a cyclic ether structure);

(2), X is a divalent straight-chain aliphatic hydrocarbon group having 6 to 20 carbon atoms, Y ¹ and Y ² are each independently a single bond, an ester bond, an amide bond or a urethane bond, R ⁴ and R ⁵ are, each independently, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, sulfo, sulfonyl group, or the formula (i) ~ a group represented by any of (vi); However, Y ¹ or Y ² is unity coalescence When R ⁴ or R ⁵ connected to Y ¹ or Y ² is not an alkyl group having 1 to 6 carbon atoms);

Wherein R ⁶ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁷ is a hydrogen atom or a methyl group, m is an integer of 0 to 6, provided that in the formula (2) of Y ¹ or Y ² when the sum is unity, m in R ⁴ or R ⁵ that is connected with a Y ¹ or Y ² is zero).

Since the positive-tone radiation-sensitive composition contains the [A] polymer and the [B] photo-acid generator, it has excellent radiation sensitivity. Incidentally, the composition includes [C] a compound represented by the formula (2) (hereinafter also referred to as a "[C] long chain alkyl group-containing compound"). With this [C] long chain alkyl group-containing compound, it is possible to improve the hydrophobicity of the cured portion with respect to the alkali developing solution and the hydrophilicity of the uncured portion with the functional group portion by the long chain alkyl group. Therefore, according to this composition, even when the conditions for forming the cured film are changed, the long chain alkyl group-containing compound [C] exhibits a buffering action and can exhibit excellent developing property and pattern forming property stably. In addition, the composition of the present invention can exhibit the light transmittance and the voltage holding ratio of the cured film obtained by including such [A] to [C] components at the same high level as that of the conventional positive radiation sensitive composition.

The [B] photoacid generator may be a compound having an oxime sulfonate group represented by the following formula (3).

(In the formula (3), R ^B1 is a linear or branched alkyl group, a cycloalkyl group or an aryl group, and some or all of the hydrogen atoms of these groups may be substituted with a substituent).

By using the compound having the above structure as the [B] photo-acid generator, the radiation sensitivity is further improved, and excellent developability and pattern forming property can be exhibited.

The positive-tone radiation-sensitive composition is suitably used for forming an interlayer insulating film of a display element. By using the positive-tone radiation-sensitive composition for forming an interlayer insulating film of a display device, an interlayer insulating film capable of meeting recent various performance demands such as high light transmittance and high voltage holding ratio can be obtained.

Further, in the method of forming the interlayer insulating film of the 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 formed in the step (1)

(3) a step of developing the coated film irradiated with the radiation in the step (2)

(4) a step of heating the developed coating film in the step (3)

Lt; / RTI >

In this method, the positive radiation-sensitive composition is used to form a pattern by exposure, development, and heating using radiation-sensitive properties, so that even when the cured film formation conditions are changed, Can be formed.

In the present specification, the "polymer" as the [A] component is a polymer having a structural unit having a group represented by the following formula (1) in one polymer molecule, and having an epoxy group- And a case in which a unit is included.

INDUSTRIAL APPLICABILITY As described above, the positive radiation-sensitive composition of the present invention contains the components [A], [B] and [C] as described above and thus has excellent radiation sensitivity and the resulting cured film has a high light transmittance and a high voltage- And is highly responsive to changes in cured film forming conditions, and can exhibit excellent developing property and pattern forming property. Therefore, the cured film obtained from the positive-tone radiation-sensitive composition of the present invention has a fine and precise pattern even when the forming conditions in the manufacturing process are changed to some extent, and has a high light transmittance and a high voltage holding ratio Therefore, it can be suitably used for an interlayer insulating film or the like.

1 is a schematic cross-sectional view showing a cured film having a contact hole.

(Mode for carrying out the invention)

The positive radiation-sensitive composition of the present invention is a positive-tone radiation-sensitive composition comprising a structural unit (hereinafter also referred to simply as "structural unit (1)") containing a group represented by the following formula (1) in the same or different polymer molecules and an epoxy group- , A [B] photo-acid generator, and [C] a long chain alkyl group-containing compound, and may further contain other optional components.

<[A] Polymer>

[A] The polymer may have structural units (1) and epoxy group-containing structural units in the same or different polymer molecules, and may have other structural units as required. Examples of the embodiment of the polymer [A] having the structural unit (1) and the epoxy group-containing structural unit are not particularly limited, and (i) both of the structural unit (1) and the epoxy group- (Ii) a polymer having a structural unit (1) in one polymer molecule and an epoxy group-containing structural unit in a different polymer molecule, and wherein in the polymer (A) (Iii) one of the polymer molecules has both of the structural unit (1) and the epoxy group-containing structural unit and the structural unit (1) in the different polymer molecule, and (I) to (iii), in the case where three polymer molecules are present in the polymer [A], the polymer [A] may be used in addition to the polymer molecules defined in During And one or more other polymer molecules are included. In any case, the effect of the present invention can be exhibited. Hereinafter, the structural unit (1), the epoxy group-containing structural unit and other structural units will be described in order.

&Lt; Structural unit (1) &gt;

In the structural unit (1), since the group represented by the formula (1) exists as a group capable of dissociating in the presence of an acid to generate a polar group (hereinafter, simply referred to as an "acid dissociable group"), The acid-dissociable group is dissociated by the acid generated from the generator, and as a result, the [A] polymer which was insoluble in alkali 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.

The alkyl group represented by R ¹ and R ² in the above formula (1) is preferably a straight chain or branched alkyl group having 1 to 30 carbon atoms and may have an oxygen atom, a sulfur atom and a nitrogen atom in the alkyl chain. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and n-octadecyl; and branched alkyl groups such as i-propyl, i-butyl, t-butyl, neopentyl, 2-hexyl and 3-hexyl groups.

The cycloalkyl group represented by R ¹ and R ² in the formula (1) is preferably a cycloalkyl group having 3 to 20 carbon atoms, and may be a polycyclic ring or may contain an oxygen atom in the ring. Specific examples of the cycloalkyl group 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.

The aryl group represented by R ¹ and R ² in the above formula (1) is preferably an aryl group having 6 to 14 carbon atoms, which may be a monocyclic ring, a monocyclic ring, or a condensed ring. Specific examples of the aryl group include a phenyl group and a naphthyl group.

Some or all of the hydrogen atoms of R &lt; ¹ &gt; and R &lt; ² &gt; may be substituted with a substituent. Examples of such a substituent include a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (the cycloalkyl group may suitably be the description of the cycloalkyl group) As the aryl group, the description of the aryl group may be suitably applied), an alkoxy group (preferably 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 (preferably an acyl group having 2 to 20 carbon atoms, such as an acetyl group, a propionyl group, , and i-butyryl group), an acyloxy group (preferably an acyloxy group having 2 to 10 carbon atoms, such as an acetoxy group, an ethylyloxy group, a butyryloxy group, a t- , t-amyloxy group and the like), alkoxy carbonyl (Preferably an alkoxycarbonyl group having 2 to 20 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group and the like), haloalkyl group (hydrogen of the above alkyl group or cycloalkyl group A group in which some or all of the atoms are substituted with halogen atoms, and examples thereof include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a fluorocyclopropyl group, and a fluorocyclobutyl group) And the like. As the cyclic structure in the aryl group, the cycloalkyl group and the like, the alkyl group can be mentioned as a new substituent.

The alkyl group, cycloalkyl group and aryl group represented by R ³ in the formula (1) can be applied to R ¹ and R ² . The aralkyl group represented by R ³ in the formula (1) is preferably an aralkyl group having 7 to 20 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group and the like. . Examples of the group represented by -M (R ^3m ) ₃ of R ^{3 in} the above formula (1) include trimethylsilanyl group, 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.

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

The structural unit (1) may have an acetal structure or a ketal structure by possessing a functional group which has an acetal structure or a ketal structure by bonding to other carbon atoms.

Examples of the functional group having an acetal structure by bonding to other carbon atoms include 1-methoxyethoxy, 1-ethoxyethoxy, 1-n-propoxyethoxy, 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) (Cyclohexyl) (ethoxy) methoxy group, (cyclohexyl) (n-propoxy) methoxy group, 1-benzyloxyethoxy group, 1-phenethyloxyethoxy group, (Cyclohexyl) (phenoxy) methoxy group, (cyclohexyl) (cyclohexyloxy) methoxy group, (cyclohexyl) (phenoxy) (Phenyl) (methoxy) methoxy group, (phenyl) (ethoxy) Methoxy group, (phenyl) (phenoxy) methoxy group, (phenyl) (i-propoxy) methoxy group, (phenyl) (cyclohexyloxy) (Benzyl) (n-propoxy) methoxy group, (benzyl) (methoxy) methoxy group, (Benzyl) (benzyloxy) methoxy group, a 2-tetrahydrofuranyloxy group, a 2-tetrahydropyranyloxy group, a benzyloxy group, , 1-trimethylsilanyloxyethoxy group, 1-trimethylgermyloxyethoxy group and the like.

Of these, preferred are 1-ethoxyethoxy group, 1-cyclohexyloxyethoxy group, 2-tetrahydropyranyloxy group, 1-n-propoxyethoxy group and 2-tetrahydropyranyloxy group have.

Examples of the functional group having a ketal structure by bonding to the above other carbon atom include 1-methyl-1-methoxyethoxy group, 1-methyl-1-ethoxyethoxy group, propoxyethoxy group, 1-methyl-1-i-butoxyethoxy group, 1-methyl-1- Methyl-1-cyclopentyloxyethoxy group, 1-methyl-1-cyclohexyloxy group, 1-methyl-1-butoxyethoxy 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, Phenyl-1-i-propoxyethoxy group, 1-phenyl-1-cyclohexyloxyethoxy group, 1-phenyl- Benzyl-1-ethoxyethoxy group, 1-benzyl-1-n-propoxy, 1-benzyl-1-ethoxyethoxy group, 1-cyclohexyloxyethoxy group, 1-benzyl-1-phenyloxyethoxy group, 1-benzyl-1-benzyloxy Ethoxy group, a 2- (2-methyl-tetrahydrofuranyl) oxy group, a 2- (2-methyl-tetrahydropyranyl) oxy group, a 1-methoxy-cyclopentyloxy group, Hexyloxy group and the like.

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

Specific examples of the structural unit (1) 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) and (1-3), R 'is a hydrogen atom or a methyl group, and R ¹ , R ² and R ³ have the same meanings as in the description of the formula (1)).

Examples of the monomer having a radically polymerizable structure (hereinafter simply referred to as &quot; the acetal structure-containing monomer &quot;) which gives the structural unit (1) represented by the above formulas (1-1) to (1-3) (Meth) acrylate, 1- (cycloalkyloxy) alkyl (meth) acrylate, 1- (haloalkoxy) alkyl (Meth) acrylate-based acetal structure-containing monomers such as pyranyl (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.

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

Specific examples of the acetal structure-containing monomer which imparts the above-mentioned structural unit (1) include, for example,

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 - (2-cyclohexylethoxy) ethyl methacrylate, 1-benzyloxyethyl methacrylate, 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) Ethyl acrylate, 1-benzyloxyethyl acrylate, 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) (1- (benzyloxy) ethoxycarbonyl) -5-norbornene, 2,3-di

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. The structural unit (1) may be used alone or in combination of two or more.

Among the acetal structure-containing monomers giving the above-mentioned constituent unit (1), among the monomers having an acetal structure, 1-ethoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 2-tetrahydropyranyl methacrylate, Methacrylate is preferred.

As the acetal structure-containing monomer imparting the structural unit (1), commercially available monomers may be used, or those synthesized by known methods may be used. For example, the acetal structure-containing monomer imparting the structural unit (1) represented by the above formula (1-1) can be synthesized by reacting (meth) acrylic acid with a vinyl ether in the presence of an acid catalyst as shown below .

(In the formula, R corresponds to a ', R ¹ and R ³ is the formula (1-1) in each R', R ¹ and R ³ and, R ²¹ and R ²² is -CH (R ²¹⁾ (R ²² ), corresponding to R ² in the formula (1-1)).

The content of the structural unit (1) 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% by mass or more and 70% by mass or less, more preferably 10% by mass or more and 60% by mass or less, based on the total structural units contained in the polymer (A) Or less, and particularly preferably 20 mass% or more and 50 mass% or less.

On the other hand, in the case where a single polymer molecule has a structural unit (1) and another single polymer molecule has an epoxy group-containing structural unit, the ratio of the structural unit (1) in the single polymer molecule having the structural unit The content is preferably from 40 mass% to 99 mass%, more preferably from 50 mass% to 98 mass%, and still more preferably from 55 mass% to 95 mass%, based on the total structural units contained in the polymer molecule % Or less is particularly preferable.

<Epoxy group-containing structural unit>

The polymer [A] has an epoxy group-containing structural unit together with the structural unit (1). The epoxy group-containing structural unit is a structural unit derived from an epoxy group-containing monomer having a radical polymerizable property. Examples of the epoxy group include an oxiranyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure). By having the polymer [A] having a structural unit including an oxiranyl group or an oxetanyl group in the molecule, the hardness of the cured film obtained from the positive-tone radiation-sensitive composition can be improved and the heat resistance can be further increased.

Specific examples of the epoxy group-containing monomer imparting the epoxy group-containing structural unit include glycidyl acrylate, glycidyl methacrylate, acrylate-3,4-epoxybutyl acrylate, Ethyl-3,4-epoxybutyl acrylate, 5,6-epoxyhexyl acrylate, methacrylic acid-5,6-epoxyhexyl methacrylate, methacrylic acid 5-ethylhexyl-5,6-epoxyhexyl, methacrylic acid-6,7-epoxyhexyl, methacrylic acid-

3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylethyl methacrylate, 3,4-epoxycyclohexylpropyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, -Epoxy cyclohexyl butyl methacrylate, 3,4-epoxycyclohexyl hexyl methacrylate, 3,4-epoxy cyclohexyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylethyl (Meth) acrylic compounds having oxirane groups such as acrylate, 3,4-epoxycyclohexylpropyl acrylate, 3,4-epoxycyclohexylbutyl acrylate and 3,4-epoxycyclohexylhexyl acrylate;

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) oxetane, 3- (acryloyloxymethyl) 3-methyloxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) Oxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -3-phenyloxetane,

3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) oxetane, 3- 3- (2-methacryloyloxyethyl) -3-methyloxetane, 3- (2-methacryloyloxyethyl) (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-phenyloxetane,

2- (acryloyloxymethyl) -2-ethyloxetane, 2- (acryloyloxymethyl) oxetane, 2- (acryloyloxymethyl) (2-acryloyloxyethyl) -2-methyloxetane, 2- (2-acryloyloxyethyl) oxetane, 2- Oxyethyl) -2-ethyloxetane, 2- (2-acryloyloxyethyl) -2-phenyloxetane,

2- (methacryloyloxymethyl) -2-ethyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- 2- (2-methacryloyloxyethyl) -2-methyloxetane, 2- (2-methacryloyloxyethyl) (Meth) acrylic compounds containing an oxetanyl group such as 2- (2-methacryloyloxyethyl) -2-ethyloxetane and 2- (2-methacryloyloxyethyl) have. The above-mentioned epoxy group-containing structural units may be used alone or in combination of two or more.

Among the epoxy group-containing monomers, glycidyl methacrylate, 2-methylglycidyl methacrylate, methacrylic acid-3,4-epoxycyclohexyl, methacrylic acid-3,4-epoxycyclohexylmethyl, 3 - (methacryloyloxymethyl) -3-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane with other radically polymerizable monomers, and a positive radiation-sensitive composition From the viewpoint of developability of the toner.

The content of the epoxy group-containing structural unit in the polymer [A] is not particularly limited as long as the desired heat resistance of the interlayer insulating film can be exhibited. When the one polymer molecule contains the structural unit (1) and the epoxy group- Is preferably 10 mass% or more and 60 mass% or less, more preferably 15 mass% or more and 55 mass% or less, and still more preferably 20 mass% or more and 50 mass% or less based on the total structural units contained in the polymer [A] Is particularly preferable.

On the other hand, when one polymer molecule has the structural unit (1) and other polymer molecules have an epoxy group-containing structural unit, the ratio of the epoxy group-containing structural units to the total structural units contained in other polymer molecules having an epoxy group- The content is preferably 20 mass% or more and 80 mass% or less, more preferably 30 mass% or more and 70 mass% or less, and particularly preferably 35 mass% or more and 65 mass% or less,

<Other structural units>

Examples of the radically polymerizable monomer that imparts other structural units include a carboxyl group or a derivative thereof, and a radically polymerizable monomer having a hydroxyl group.

Examples of the radical polymer monomer having a carboxyl group or a derivative thereof include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, 2-acryloyloxyethylhexahydro Monocarboxylic acids such as phthalic 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.

As examples of the radically polymerizable monomer having a hydroxyl group,

Acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and 4-hydroxymethylcyclohexylmethyl acrylate;

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 radical polymerizable monomers having hydroxyl groups, from the viewpoints of the copolymerization reactivity with other radical polymerizable monomers and the heat resistance of the obtained interlayer insulating film, it is preferable to use acrylic acid-2-hydroxyethyl ester, 4-hydroxybutyl ester, methacrylic acid-2-hydroxyethyl ester, methacrylic acid-4-hydroxybutyl ester, 4-hydroxymethyl-cyclohexylmethyl acrylate, methacrylic acid- Methyl-cyclohexyl methyl ester is preferred.

Examples of other radically polymerizable monomers include,

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 other radical polymerizable 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. From the viewpoint of copolymerization reactivity with the radically polymerizable monomer having a carboxyl group and the developability of the positive-tone radiation-sensitive composition.

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

The polystyrene reduced number average molecular weight (hereinafter referred to as &quot; Mn &quot;) of the polymer [A] by GPC (gel permeation chromatography) is preferably 2.0 x 10 ^{3 to} 1.0 x 10 ⁵ , more preferably 5.0 × 10 ^{3 to} 5.0 × 10 ⁴ . By setting the Mn of the copolymer within the above range, the curing reactivity upon curing of the coating film of the positive radiation-sensitive composition can be improved.

The molecular weight distribution &quot; Mw / Mn &quot; 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 can be enhanced. The positive-tone radiation-sensitive composition containing the polymer [A] can easily form a desired pattern shape without causing development residue during development.

&Lt; Process for producing [A] polymer &gt;

The polymer [A] can be produced by radical copolymerization of an acetal structure-containing monomer, an epoxy group-containing monomer and a monomer giving another structural unit. When the polymer [A] containing both the structural unit (1) and the epoxy group-containing structural unit is produced in the same polymer molecule, it may be copolymerized using a mixture containing at least an acetal structure-containing monomer and an epoxy group-containing monomer. On the other hand, in the case of producing a polymer [A] having a structural unit (1) in one polymer molecule and an epoxy group-containing structural unit in a polymer molecule different therefrom, the polymerizable solution containing at least an acetal structure- To obtain a polymer molecule having the structural unit (1), and at least a polymerizable solution containing at least an epoxy group-containing monomer is radically polymerized to obtain a polymer molecule having an epoxy group-containing structural unit, and finally, A] polymer.

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

As these solvents,

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;

As the glycol ether, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like;

As the ethylene glycol alkyl ether acetate, for example, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate and the like;

As the diethylene glycol alkyl ether, for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and the like;

As the propylene glycol monoalkyl ether, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like;

As the propylene glycol monoalkyl ether acetate, for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate and the like;

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

As aromatic hydrocarbons, for example, toluene, xylene and the like;

As the ketone, for example, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and the like;

Examples of other esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy- Hydroxypropionate, propyl 3-hydroxypropionate, propyl 3-hydroxypropionate, propyl 3-hydroxypropionate, propyl 3-hydroxypropionate, propyl 3-hydroxypropionate, Propyl methoxyacetate, butyl hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, ethyl ethoxyacetate, ethoxyacetic acid Propyl, 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, 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- Ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, A field, 3-propoxy propionate, butyl propionate, methyl 3-butoxy, 3-butoxy-ethyl, 3-butoxy propyl propionate, butyl propionate, 3-butoxy, etc. of esters there may be mentioned, respectively.

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

As the polymerization initiator used in the polymerization reaction for producing the polymer [A], those generally known as radical polymerization initiators can be used. As the radical polymerization initiator, for example,

(2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4-dimethyl Azo compounds such as 2,2'-azobis (methyl 2-methylpropionate);

Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxy pivalate, 1,1'-bis- (t-butylperoxy) cyclohexane; And hydrogen peroxide.

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

In the polymerization reaction for producing the polymer [A], a molecular weight regulator may be used to adjust the molecular weight. As specific examples of the molecular weight adjuster,

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;

Azotrienols such as dimethylguanidine sulfide, diisopropylguanogen sulfide and the like;

Terpinolene, alpha -methylstyrene dimer, and the like.

<[B] Mineral Generator>

[B] The photoacid generator is a compound which generates an acid upon irradiation with radiation. As the radiation, visible rays, ultraviolet rays, far ultraviolet rays, and the like can be used. When the composition contains a [A] polymer having a [B] photo-acid generator and an acid-dissociable group, a positive radiation-sensitive property can be exhibited. The [B] photoacid generator is not particularly limited as long as it is a compound which generates an acid (for example, a carboxylic acid, a sulfonic acid, or the like) upon irradiation with radiation. The form of the [B] photoacid generator in the composition may be in the form of a photoacid generator (hereinafter sometimes referred to as "[B] photoacid generator") which is a compound to be described later, Or may be in the form of a photo-acid generator incorporated as a part of the polymer, or in both of them.

Examples of the [B] photoacid generator include an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonate esterified compound and a carbonic acid ester compound.

(Oxime sulfonate compound)

As the oxime sulfonate compound, a compound containing an oxime sulfonate group represented by the formula (3) is preferable.

As the straight chain or branched alkyl group represented by R ^B1 , a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. A part or all of the hydrogen atoms of the straight chain or branched alkyl group or cycloalkyl group represented by R ^B1 is an alkoxy group having 1 to 10 carbon atoms or an alicyclic group (such as a 7,7-dimethyl-2-oxonorbornyl group, (Including bridged) alicyclic groups, preferably a bicycloalkyl group, etc.). 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 of R ^B1 may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group, or a halogen atom.

It is more preferable that the compound containing an oxime sulfonate group represented by the formula (3) is an oxime sulfonate compound represented by the following formula (3-1).

In the formula (3-1), R ^B1 is a description of the same meaning of R ^B1 in the formula (3). Z is an alkyl group, an alkoxy group, or a halogen atom. M is an integer of 0 to 3; When m is 2 or 3, plural Zs may be the same or different. The alkyl group as Z is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

As the alkoxy group as Z, a straight-chain or branched alkoxy group having 1 to 4 carbon atoms is preferable. The halogen atom as Z is preferably a chlorine atom or a fluorine atom. M is preferably 0 or 1. Particularly, a compound in which m is 1, Z is a methyl group, and Z is a substituted position in the formula (3-1) is preferable.

Specific examples of the oxime sulfonate compound include compounds (3-i), (3-ii), (3-iii), Compounds (3-iv) and (3-v).

These acid generators may be used singly or in combination of two or more, and may be used in combination with other photoacid generators as the [B] component. (3-i) [(5-propylsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile] (3-iii) [(camphorsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile] -Methylphenyl) acetonitrile], the compound (3-iv) [(5-p-toluenesulfonyloxyimino-5H-thiophen- ) [(5-octylsulfonyloxyimino) - (4-methoxyphenyl) acetonitrile] is commercially available.

(Onium salt)

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 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 Butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium- Sulfonate, bis (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 alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts and substituted benzylsulfonium salts.

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-butoxynaphthalene- 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-1,1,2,2-tetrafluoro-2- (norbornan- (5-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoro-2- (6-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) -benzenesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophene- ) -1,1,2,2-tetrafluoroethanesulfonate, and the like.

(Sulfonimide compound)

Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide , N- (2-trifluoromethylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- - (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- Methylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphenylmaleimide, 4-methylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) Maleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (phenylsulfonyloxy) bicyclo [2.2. 1] hept-5-en-2 , 3-dicarboxyimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethanesulfonyloxy) Cyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (nonafluorobutanesulfonyloxy) bicyclo [2.2.1] hept- (Camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid, N- (camphorsulfonyloxy) bicyclo [ 2,1-hept-5-ene-2,3-dicarboxylic imide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2. 1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hepto- N- (2-trifluoromethylphen &lt; / RTI &gt; 2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] 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-fluorophenyl) naphthyldicarbamylimide, N- (Pentafluoroethylsulfonyloxy) naphthyldicarboxylic imide, N- (heptafluoropropylsulfonyloxy) naphthyldicarboxyimide, N- (nonafluoro-sulfonyloxy) (Propylsulfonyloxy) naphthyldicarboxylic imide, N- (butylsulfonyloxy) naphthyldicarbide, N-ethylsulfonyloxy) naphthyldicarbamylimide, N- (Hexylsulfonyloxy) naphthyldicarboxylic imide, N- (heptylsulfonyloxy) naphthyldicarboxylimide, N- (pentylsulfonyloxy) naphthyldicarboxylic imide, N- Naphthyldicarboxylic imide, and N- (nonylsulfonyloxy) naphthyldicarboxylimide.

(Halogen-containing compound)

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

(Diazomethane compound)

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

(Sulfone compound)

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

(Sulfonic acid ester compound)

Examples of the sulfonic acid ester compound include alkylsulfonic acid esters, haloalkylsulfonic acid esters, arylsulfonic acid esters, iminosulfonates, and the like.

(Carbonic acid ester compound)

As the carbonic acid ester compound, for example, carbonic acid o-nitrobenzyl ester can be mentioned.

Among these [B] photoacid generators, oxime sulfonate compounds are preferable from the viewpoints of radiation sensitivity and solubility in solvents, compounds containing oxime sulfonate groups represented by the above formula (3) are more preferable, The oximesulfonate compound represented by the above formula (3-1) is more preferable, and among them, [(5-propylsulfonyloxyimino-5H-thiophen-2-ylidene) - (2- Methylphenyl) acetonitrile], [(5-octylsulfonyloxyimino-5H-thiophen-2-ylidene) - Thiophen-2-ylidene) - (2-methylphenyl) acetonitrile], [(5-methylphenyl) acetonitrile] Octylsulfonyloxyimino) - (4-methoxyphenyl) acetonitrile] are particularly preferred.

Onium salts are also preferable, and tetrahydrothiophenium salts and benzylsulfonium salts are more preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate and benzyl- 4-hydroxyphenylmethylsulfonium hexafluorophosphate is particularly preferred.

As the [B] photo-acid generator, one type may be used alone, or two or more types may be used in combination. The content of the [B] photoacid generator in the composition is preferably 0.1 part by mass to 10 parts by mass, more preferably 1 part by mass to 5 parts by mass, based on 100 parts by mass of the polymer [A]. When the content of the [B] photo-acid generator is in the above range, the radiation sensitivity of the composition is optimized, and an interlayer insulating film having a high voltage holding ratio can be formed while maintaining transparency.

<[C] Long chain alkyl group-containing compound>

The [C] long chain alkyl group-containing compound is a compound represented by the above formula (2), specifically, X (divalent straight chain aliphatic hydrocarbon group having 6 to 20 carbon atoms), which exhibits hydrophobicity in one molecule, Lt; / RTI &gt;

The [C] long chain alkyl group-containing compound reacts with a part of the [A] component using heating or an alkali component in the developer as a catalyst, so that the hardness and density of the cured film can be improved. By improving the hardness and density of the cured film, resistance to various kinds of resistances such as acid, alkali aqueous solution, organic solvent, etching gas and the like is improved, and a remarkable effect can be exhibited in suppressing pattern defects.

Furthermore, since the [C] component reacted with a part of the [A] component has a long-chain alkyl group exhibiting hydrophobicity, the hydrophobicity of the cured portion to the alkali developer is improved. On the other hand, since the functional group of the unreacted [C] component is hydrophilic, the hydrophilic property of the uncured portion can be exerted. Therefore, according to this composition, even when the conditions for forming the cured film are changed such as pre-baking at a low temperature or an increase in development time, the long-chain alkyl group-containing compound [C] exhibits a buffering action, Can be stably exhibited.

Also, even if the content of the component [C] is contained, the effect on the light transmittance and the voltage holding ratio of the obtained cured film is small, and the cured film obtained from the composition can exhibit a high light transmittance and a voltage holding ratio.

When the carbon number of X is 5 or less, the hydrophilicity of both ends or one end is strongly expressed, so that the development ability is excessively promoted. Conversely, when the number of carbon atoms of X is 21 or more, Resulting in the development of residual phenomena and the like.

X is a divalent straight-chain aliphatic hydrocarbon group having 6 to 20 carbon atoms, but is preferably a divalent alkylene group having 6 to 20 carbon atoms and not containing an unsaturated bond. The straight-chain aliphatic hydrocarbon group may be substituted with a part or all of the hydrogen atoms.

As specific examples of the [C] component, there may be mentioned, for example, the following fatty acids, alcohols, esters, sulfonic acids, and epoxy compounds.

Examples of the fatty acid having a divalent straight-chain aliphatic hydrocarbon group having 6 to 20 carbon atoms include caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, Linolenic acid, linolenic acid, eleostearic acid, fumaric acid, palmitoleic acid, palmitoleic acid, margaric acid, stearic acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid, , Tuberculostearic acid, arachidic acid, arachidonic acid, decanedioic acid, hexadecanedioic acid, heptadecanedioic acid, nonadecanedioic acid, octadecanedioic acid, octadecanedioic acid, , Pentadecanedioic acid, tridecanedioic acid, tetradecanedioic acid, glycidyl stearate, glycidyl palmitate, cis-9-hexadecenoic acid, and elaidic acid.

Examples of the divalent straight chain aliphatic hydrocarbon group having 6 to 20 carbon atoms include n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-nonyl alcohol, n-decyl alcohol, octadecanol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, trans-9-octadecenol, oleyl alcohol, trans-2-dodecenol, and the like.

Examples of esters having a divalent straight chain aliphatic hydrocarbon group having 6 to 20 carbon atoms include methyl caprylate, ethyl caprylate, methyl pelargonate, ethyl pelargonate, methyl caprate, caprylate, lauric acid And examples thereof include methyl, ethyl laurate, methyl myristate, methyl pentadecylate, methyl palmitate, methyl palmitoleate, methyl margarate, methyl stearate, methyl oleate, methyl myristate, methyl linoleate, methyl linolenate, Methyl stearate, methyl stearate, methyl stearate, methyl arachidonate, and methyl arachidonate.

Examples of the sulfonic acid having a divalent straight-chain aliphatic hydrocarbon group having 6 to 20 carbon atoms include 1-dodecane sulfonic acid, 1-undecane sulfonic acid, dodecylbenzene sulfonic acid and 1-nonane sulfonic acid.

As the epoxy compound having a divalent straight-chain aliphatic hydrocarbon group having 6 to 20 carbon atoms (a compound represented by any one of the above formulas (i) to (iii) as R ⁴ and / or R ⁵ )

1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2-epoxydecane, 1,2-epoxyheptadecane, 1,2-epoxynonadecane, 1,2- epoxy pentadecane, the compound is a glycidyl stearate, glycidyl palmitate, R ⁴ and / or R ^5, such as dill, represented by the above formula (i),

1- (3,4-epoxycyclohexyl) -decane, 1- (3,4-epoxycyclohexyl) -dodecane, 1- - epoxycyclohexyl) - compound is R ⁴ and / or R ^5, such as hexadecane, represented by the above formula (ii),

R ⁴ and / or R ⁵ such as 3-octyloxetane, 3-ethyl-3-octyloxetane, 3-nonyloxetane and 3-ethyl-

.

When the component [C] is an epoxy compound (a compound in which R ⁴ and / or R ⁵ is represented by any one of the above formulas (i) to (iii)), the polymer [A] C] component can bond particularly strongly, a synergistic effect of the density and hydrophobicity of the cured film is remarkable. Therefore, when an epoxy compound is used as the [C] component, the changeability of the cured film forming conditions of the composition is further improved, and more excellent developability and pattern forming property can be exhibited.

Examples of the [C] long chain alkyl group-containing compound include compounds having an urethane group obtained by reacting a compound having an isocyanate group and a compound having a hydroxyl group, compounds having an amide group obtained by a reaction between a compound having an amino group and a compound having a carboxyl group, And compounds having an ester group obtained by the reaction of a compound having a group and a compound having a hydroxyl group. Specific examples of such a compound include compounds represented by the following formulas (2-1) to (2-4) have.

Among the above-mentioned [C] long chain alkyl group-containing compounds, from the viewpoint of developability and pattern forming property, fatty acids such as palmitic acid, stearic acid and tetradecanedioic acid, alcohols such as 1-dodecanol, 1,12-dodecanediol, Epoxy compounds such as 1,2-epoxytetradecane, 1,2-epoxyhexadecane, glycidyl stearate and 1,3-epoxy-2-ethyl-2-dodecane, sulfonic acid of 1-dodecane sulfonic acid, desirable.

The [C] long chain alkyl group-containing compounds may be used alone or in combination of two or more. The amount of the [C] long chain alkyl group-containing compound in the radiation sensitive composition is preferably from 0.01 to 20 parts by mass, more preferably from 0.05 to 15 parts by mass, based on 100 parts by mass of the polymer [A]. By setting the amount of the [C] long chain alkyl group-containing compound to fall within the above range, developability and pattern forming property can be effectively exerted even when the cured film forming conditions are changed.

&Lt; Other optional components &gt;

The positive radiation-sensitive composition of the present invention may contain, in addition to the above components [A] to [C], a surfactant [D] F] basic compounds, quinone diazide compounds, and the like.

&Lt; [D] Surfactant &gt;

The surfactant can be used to further improve the film formability of the composition. Examples of such surfactants include fluorine-based surfactants, silicone-based surfactants, and other surfactants. When the composition contains the [D] surfactant, the surface smoothness of the coating film can be improved, and as a result, the uniformity of the film thickness of the formed interlayer insulating film can be further improved.

As the fluorine-containing 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. Examples of the fluorine-based surfactant include 1,1,2,2-tetrafluoro-n-octyl (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2 Hexafluoro-n-hexyl ether, hexaethylene glycol di (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, octaethylene glycol di , 2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycol di , 2,2-tetrafluoro-n-butyl) ether, sodium perfluoro-n-dodecanesulfonate, 1,1,2,2,3,3-hexafluoro-n- 2,2,3,3,9,9,10,10-decafluoro-n-dodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarbonate, diglycerin tetrakis ( Fluoroalkyl polyoxyethylene ether), fluoroalkylammonium iodide, fluoroalkyl betaine, fluoroalkyl polyoxyethylene ether, perfluoro To kill roal polyoxyethylene ethanol, alkyl alkoxylate, a carbonic acid-fluoro-perfluoroalkyl, and the like esters.

Examples of commercially available products of the fluorinated surfactants include BM-1000, BM-1100 (manufactured by BM CHEMIE), Megaface F142D, Megafac F172, Megafac F173, Megafac F183, Fluorad FC-170C, Fluorad FC-171, Fluorad FC-430, Fluorad FC-170, and Fluorad FC- Surflon S-112, Surplon S-113, Surplon S-131, Surplon S-141, Surplon S-145, Surplon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC- 106 (available from Asahi Glass Co., Ltd.), Eftop Ftergent FT-100, Ftergent FT-110, Ftergent FT-140A, Ftergent FT-150, Fotogent FT-100, FT-250, Fotent FT-251, Gentry may include FT-300, such as printers Gentry FT-310, FT-400S Gentry printers, printers Gentry FTX-218, printers Gentry FT-251 (above, whether or manufactured by Neos).

Examples of the silicone surfactant include silicone oils such as Toray silicone DC3PA, Toresilicon DC7PA, Toresilicon SH11PA, Toresilicon SH21PA, Toresilicon SH28PA, Toresilicon SH29PA, Toresilicon SH30PA, Toresilicon SH- (Manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300 (available from Toray Silicone Co., Ltd.), Toray Silicon SZ-603, Toray Silicon SF- , TSF-4445, TSF-4446, TSF-4460, TSF-4452 (manufactured by GE Toshiba Silicone Co., Ltd.), and organosiloxane polymer KP341 (Shinetsu Kagakukogyo Co., Ltd.).

These [D] surfactants may be used singly or in combination of two or more kinds. The content of the [D] surfactant in the composition is preferably 0.01 parts by mass or more and 2 parts by mass or less, more preferably 0.05 parts by mass or more and 1 part by mass or less, based on 100 parts by mass of the polymer [A] . By setting the content of the [D] surfactant within the above range, the surface smoothness of the coating film can be further improved.

<[E] Adhesion aid>

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, ] Can be used. As such an adhesion auxiliary agent, 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.

Specific examples of the functional silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane, Glycidoxypropylalkyldialkoxysilane,? -Chloropropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? - Ethoxy silane, and the like. Among these,? -Glycidoxypropylalkyldialkoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane and? -Methacryloxypropyltrimethoxysilane are preferable.

In the positive-tone radiation-sensitive composition, the amount of the [E] adhesion aid is preferably 0.5 part 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 less, Or less. When the amount of the [E] adhesion aid is in the above range, adhesion between the interlayer insulating film and the substrate is improved.

&Lt; [F] Basic compound &gt;

The basic compound can be arbitrarily selected from chemical amplification resistors. Examples of the basic compound include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium carbonates. By containing a basic compound as the [F] component in the positive-tone radiation-sensitive composition, the diffusion length of the acid generated from the photoacid generator by exposure can be appropriately controlled, and the pattern developability can be improved.

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

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

Examples of heterocyclic amines include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, Benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8- Diazabicyclo [4,3,0] -5- (4,3, 4, 5-tetramethylpiperazin-1-yl) quinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, Nonene, 1,8-diazabicyclo [5,3,0] -7-undecene, and the like.

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

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

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

&Lt; Quinone diazide compound &gt;

The quinone diazide compound is a compound which generates carbonic acid by irradiation with radiation. As the quinone diazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter 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.

As the tetrahydroxybenzophenone, for example, 2,2'4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetra Hydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, and 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone. .

Examples of the pentahydroxybenzophenone include 2,3,4,2'6'-pentahydroxybenzophenone and the like.

As the hexahydroxybenzophenone, for example, 2,4,6,3'4'5'-hexahydroxybenzophenone, 3,4,5,3'4'5'-hexahydroxybenzophenone, etc., .

(P-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1 (p-hydroxyphenyl) -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, and the like.

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-naphthoquinonediazidesulfonic 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 and 1,2-naphthoquinonediazide-5-sulfonic acid chloride. Among them, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is preferable.

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

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

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

&Lt; Positive radiation sensitive composition &gt;

The positive radiation-sensitive composition of the present invention is prepared by mixing the aforementioned polymer [A], the [B] photo-acid generator, the [C] long chain alkyl group-containing compound and, if necessary, optional components. The positive-tone radiation-sensitive composition may preferably be prepared by dissolving or dispersing in a suitable solvent. For example, the positive radiation-sensitive composition can be prepared by mixing the components [A], [B] and [C] and optional components in a predetermined ratio in a solvent.

<Solvent>

As the solvent which can be used for the preparation of the positive-tone radiation-sensitive composition, those which do not react with each component by uniformly dissolving or dispersing the components are suitably used. Examples of such a solvent include alcohols, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionate Aromatic hydrocarbons, ketones, esters, and the like.

As these solvents,

As the alcohols, for example, benzyl alcohol, diacetone alcohol and the like;

As the ether, for example, dialkyl ethers such as tetrahydrofuran, diisopropyl ether, di-n-butyl ether, di-n-pentyl ether, diisopentyl ether and di-n-hexyl ether;

Examples of diethylene glycol alkyl ethers include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether;

As the ethylene glycol alkyl ether acetates, for example, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate and the like;

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

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

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

As aromatic hydrocarbons, for example, toluene, xylene and the like;

As the ketone, for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone and the like;

Examples of esters include methyl acetate, ethyl acetate, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy- Hydroxypropionate, ethyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, Propyl methoxyacetate, propyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetate , Ethoxyacetic acid propyl acetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, Propoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, , Butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, and the like.

Of these solvents, ethers such as dialkyl ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, and the like are preferable from the viewpoints of excellent solubility or dispersibility, non-reactivity with each component, 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 , 2-hydroxy-2-methylpropionic acid , The 2-hydroxy-2-methylpropionic acid ethyl, methyl lactate, ethyl lactate, propyl lactate, butyl, 2-methoxy-propionic acid methyl, 2-methoxy-propionic acid ethyl are preferred. These solvents may be used alone or in combination.

Among these solvents, ethers such as diisopropyl ether, di-n-butyl ether, di-n-pentyl ether, diisopentyl ether and dialkyl ethers such as di-n-hexyl ether are preferable, Most preferred is isopentyl ether. By using such a solvent, when the radiation sensitive composition is applied to a large glass substrate by the slit coating method, the drying process time can be shortened and the coating property can be further improved (coating irregularity can be suppressed).

In addition to the above-mentioned preferred solvents, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetonyl acetone, isophorone, capro Examples of the organic solvent include acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, Acetate, carbitol acetate, and the like may be used in combination.

When the positive-tone radiation-sensitive composition is prepared in the form of a solution or dispersion, the ratio of the components other than the solvent (i.e., the total amount of the [A], the [B] and the component [C] But it is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 35% by mass.

&Lt; Formation of a cured film such as an interlayer insulating film &

Next, a method of forming a cured film such as an interlayer insulating film on a substrate using the above positive radiation sensitive composition will be described.

The method comprises:

(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 formed in the step (1)

(3) a step of developing the coated film irradiated with the radiation in the step (2)

(4) a step of heating the developed coating film in the step (3)

Respectively.

&Lt; (1) Step of forming a coating film of positive-tone radiation-sensitive composition on a substrate &

In the step (1), the positive-tone radiation-sensitive composition or the solution or dispersion is applied onto the substrate, and then the coated surface is preferably heated (prebaked) to remove the solvent to form a coated film. Examples of the substrate that can be used include glass, quartz, silicon, resin and the like. Specific 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 method of applying the composition solution or dispersion is not particularly limited and an appropriate method such as a spray method, a roll coating method, a rotation coating method (spin coating method), a slit die coating method or a bar coating method can be employed . Of these coating methods, a spin coating method or a slit die coating method is preferable. The conditions of the prebaking vary depending on the kind of each component, the blending ratio, and the like, but can be preferably about 60 to 120 DEG C for about 1 to 10 minutes. According to the positive radiation-sensitive composition of the present invention, even when the pre-baking conditions are relatively low, for example, 60 to 80 캜, excellent pattern-forming properties can be exhibited.

&Lt; (2) Step of irradiating at least part of the coating film with radiation &

In the step (2), at least a part of the formed coating film is exposed. In this case, when a part of the coating film is exposed, exposure is usually performed through a photomask having a predetermined pattern. As the radiation used for exposure, radiation used for the photo-acid generator is suitable. Of these radiation, radiation having a wavelength in the range of 190 to 450 nm is preferable, and radiation containing ultraviolet radiation of 365 nm in particular is preferable.

The exposure dose in the process is preferably from 500 to 6,000 J / m 2, more preferably from 500 to 6,000 J / m 2, as measured by an illuminometer (OAI model 356, manufactured by OAI Optical Associates Inc.) at a wavelength of 365 nm Is 1,500 to 1,800 J / m &lt; 2 &gt;.

&Lt; (3) Developing process &gt;

In the step (3), the coating film after exposure is developed to remove unnecessary portions (irradiated portions of radiation) 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 such an 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. As the developing method, suitable methods such as puddle method, dipping method, swing dipping method, and shower method can be used. The developing time varies depending on the composition of the positive-tone radiation-sensitive composition, but is preferably about 10 to 180 seconds. Further, according to this composition, a stable pattern can be formed even if there are some advantages or disadvantages in the developing time, without being affected by this. Following this developing treatment, for example, water washing is carried out for 30 to 90 seconds, and then air is blown with, for example, compressed air or compressed nitrogen, whereby a desired pattern can be formed.

&Lt; (4) Heating process &gt;

In the step (4), the patterned thin film is heated by using a heating device such as a hot plate or an oven to accelerate the curing reaction of the component [A] to obtain a cured product. The heating temperature in this step is, for example, 120 to 250 占 폚. The heating time varies depending on the type of the heating apparatus. For example, the heating time may be 5 to 30 minutes in the case of performing the heating process on the hot plate, and 30 to 90 minutes in the case of performing the heating process in the oven. A step baking method in which two or more heating steps are performed, or the like may be used. In this manner, a patterned thin film corresponding to a target interlayer insulating film or the like can be formed on the surface of the substrate.

&Lt; Cured film such as an interlayer insulating film &

The film thickness of the cured film such as an interlayer insulating film formed in this way is preferably 0.1 to 8 占 퐉, more preferably 0.1 to 6 占 퐉, and still more preferably 0.1 to 4 占 퐉.

The interlayer insulating film formed of the positive radiation sensitive composition of the present invention has excellent pattern forming properties while having a high light transmittance and a high voltage holding ratio as apparent from the following examples. Therefore, the cured film can be used for an interlayer insulating film, a spacer, a protective film or the like of a display element, and is particularly suitably used as an interlayer insulating film of a display element.

(Example)

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Hereinafter, the mass average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer were measured by gel permeation chromatography (GPC) under the following conditions.

Apparatus: GPC-101 (manufactured by Showa Denko K.K.)

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

<Synthesis Example of [A] Polymer>

[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, -Methylstyrene dimer in an amount of 3 parts by mass, the mixture was purged with nitrogen, and stirring was started slowly. 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 weight average molecular weight (Mw) of the polymer (A-1) in terms of polystyrene was 9,000. The solid concentration of the polymer solution thus obtained (the ratio of the mass of the polymer contained in the polymer solution in the total mass of the polymer solution, hereinafter the same) 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 mass parts of methacrylic acid, 40 mass parts of tetrahydro-2H-pyran-2-yl methacrylate, 5 mass parts of styrene, 40 mass parts of glycidyl methacrylate, 10 mass parts of 2-hydroxyethyl methacrylate And 3 parts by mass of? -Methylstyrene dimer were put in a flask, and after the flask was purged with nitrogen, stirring was started slowly. 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 weight average molecular weight (Mw) of the polymer (A-2) in terms of polystyrene was 9,000. The polymer solution thus obtained had a solid concentration of 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, and stirring was started slowly. 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 weight average molecular weight (Mw) of the polymer (a-1) in terms of polystyrene was 9,000. The solid concentration of the polymer solution obtained here was 30.3% by 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 charged and replaced with nitrogen, and then stirring was started slowly. 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 weight average molecular weight (Mw) of the polymer (a-2) in terms of polystyrene was 9,000. The solid solution concentration of the polymer solution obtained here 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 tetrahydro-2H-pyran-2-yl methacrylate, 7 parts by mass of 2-hydroxyethyl methacrylate and 8 parts by mass of methacrylic acid were purged with nitrogen, and stirring was started slowly. 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 polystyrene reduced mass average molecular weight (Mw) of the polymer (a-3) was 10,000. The solid solution concentration of the polymer solution obtained here 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, and stirring was started slowly. 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 mass average molecular weight (Mw) of the polymer (aa-1) in terms of polystyrene was 10,000. The solid concentration of the polymer solution obtained here was 32.3% by 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 purged with nitrogen, and stirring was started slowly. 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 weight average molecular weight (Mw) of the polymer (aa-2) in terms of polystyrene was 10,000. The solid concentration of the polymer solution obtained here was 33.2 mass%.

[Synthesis Example 8]

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, 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 stirring was started slowly. 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 weight average molecular weight (Mw) of the polymer (aa-3) in terms of polystyrene was 10,000. The solid concentration of the polymer solution obtained here was 32.3% by mass.

[Preparation of positive-tone radiation-sensitive composition]

The components in Table 1 used in Examples and Comparative Examples are as follows.

(B) Component [

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] represented by the above compound (3-i) (manufactured by Chiba Specialty Chemicals Co., Quot; IRGACURE PAG 103 &quot;, manufactured by Shikisai Co., Ltd.)

B-4: [(5-Octylsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile] represented by the above compound (3-ii) (manufactured by Chiba Specialty Chemicals Co., IRGACURE PAG 108 &quot; manufactured by Shikisai Co., Ltd.)

(5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile represented by the above-mentioned compound (3-iv) (manufactured by Chiba Specialty Chemicals Quot; IRGACURE PAG 121 &quot;, manufactured by ZEON Corporation)

B-6: [(Camphorsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile] represented by the above-mentioned compound (3-iii) (manufactured by Chiba Specialty Chemicals Co., &Quot; CGI 1380 &quot;

B-7: [(5-Octylsulfonyloxyimino) - (4-methoxyphenyl) acetonitrile] (CGI725 manufactured by Chiba Specialty Chemicals Co., Ltd.) represented by the above compound (3-v)

Component (C) The long-chain alkyl group-containing compound

C-1: Palmitic acid

C-2: Stearic acid

C-3: tetradecanedioic acid

C-4: 1-Dodecanol

C-5: 1,12-Dodecanediol

C-6: 1,2-epoxytetradecane

C-7: 1,2-epoxy hexadecane

C-8: Glycidyl stearate

C-9: 3-ethyl-3-nonyloxetane

C-10: 1-Dodecane sulfonic acid

C'-1: acid _{(CH 3 (CH 2) 3} COOH)

C'-2: serine lignoceric acid _{(CH 3 (CH 2) 22} COOH)

C'-3: Nose league reel alcohol _{(CH 3 (CH 2) 23} OH)

(D) Component Surfactant

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

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

(E) Component Adhesion Adjuvant

E-1:? -Glycidoxypropyltrimethoxysilane

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

E-3:? -Methacryloxypropyltrimethoxysilane

(F) Component [

F-1: 4-Dimethylaminopyridine

F-2: 1,5-Diazabicyclo [4.3.0] -5-nonene

[Example 1]

(B-4) was used as the [B] component in a solution (100 parts by mass (solid content) of the polymer (A-1)) containing the polymer (A- (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile] (manufactured by Chiba Specialty Chemicals Co., Ltd.) represented by the above compound (3-ii) 4 parts by mass of (C-1) palmitoic acid as the [C] component, 3 parts by mass of the silicone surfactant (D-1) , 0.20 parts by mass of "SH 8400 FLUID" as the component (E), and 3.0 parts by mass of (E-1) -glycidoxypropyltrimethoxysilane as the [E] component were filtered and filtered through a membrane filter having a pore size of 0.2 μm to obtain a positive- A composition was prepared.

[Examples 2 to 10 and Comparative Examples 1 to 7]

The positive radiation-sensitive compositions of Examples 2 to 10 and Comparative Examples 1 to 7 were prepared in the same manner as in Example 1, except that the kinds and amounts of the respective components were changed as shown in Table 1.

&Lt; Evaluation of physical properties &

Each of the positive radiation-sensitive compositions prepared as described above was used to evaluate various properties of the composition and its coating film or interlayer insulating film as follows.

(1) Radiation sensitivity

Hexamethyldisilazane (HMDS) was applied onto a chromium-deposited glass of 550 x 650 mm and heated at 60 占 폚 for 1 minute (HMDS treatment). The radiation sensitive composition prepared as described above was coated on the chromium-deposited glass after the HMDS treatment using a slit die coater &quot; TR632105-CL &quot;, and the solvent was removed under vacuum with the ultimate pressure set at 100 Pa. Lt; 0 &gt; C for 2 minutes to form a coating film having a film thickness of 3.0 m. Subsequently, using a MPA-600FA exposure machine manufactured by Canon Kabushiki Kaisha, the coating film was irradiated with radiation with varying exposure dose through a mask having a 60 占 퐉 line-and-space (10: 1) pattern , And the aqueous solution of tetramethylammonium hydroxide at the concentration shown in Table 1 was developed by the puddle method at 25 ° C. Here, the development time was 80 seconds when a developer having a tetramethylammonium hydroxide concentration of 0.40% by mass was used, and 50 seconds when a developer with 2.38% by mass was used. 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 amount of exposure required to completely dissolve the space pattern of 6 mu m was examined. This value is shown in Table 1 as the radiation sensitivity. When this value is 500 J / m &lt; 2 &gt; or less, it can be said that the sensitivity is good.

(2) Shape stability of contact hole

Coated on a silicon substrate using a spinner, and then pre-baked on a hot plate under two conditions of prebaking at 70 캜 for 3 minutes and 90 캜 for 3 minutes to form a film having a film thickness of 3.0 탆 . Using a PLA-501F exposure apparatus (ultrahigh-pressure mercury lamp) manufactured by Canon Kabushiki Kaisha, exposure of a coating film was carried out through a mask of contact hole pattern of 10 mu m x 10 mu m at the required exposure amount evaluated in evaluation of radiation sensitivity (1) . Subsequently, development processing was carried out at 25 占 폚 by a puddle method using a tetramethylammonium hydroxide aqueous solution (developing solution) having a concentration of 0.4 mass%. The development processing time was set to 100 seconds. After the developing treatment, the coating film was washed with water by ultra pure water for 1 minute and dried to form a contact hole pattern on the wafer. The formed pattern was observed by SEM (scanning electron microscope).

In the case where there is no difference in the contact hole pattern prepared by two conditions of the prebaking temperature of 70 캜 for 3 minutes and the prebaking temperature of 90 캜 for 3 minutes, the shape stability of the contact hole with respect to the temperature change of the prebaking is high, And the pattern forming property can be said to be good. On the other hand, when the size of the contact hole is significantly changed or peeling from the substrate occurs with respect to the change of the prebaking temperature, the shape stability of the contact hole with respect to the temperature change of the prebaking is low, .

(Evaluation standard)

Sectional view of the cured film 2 having the contact hole 3 formed on the substrate 1 shown in Fig. 1 was determined by the following evaluation criteria.

In the case of the contact hole shape shown in Fig. 1 (a), it was judged to be good (indicated by A).

- It was judged that the shape of the contact hole was bad when the shape of the contact hole was greatly enlarged as in the case of Fig. 1 (b) (indicated by B).

The shape of the contact hole was judged to be defective (indicated by C), as in the case of Fig. The results are shown in Table 1.

(3) Light transmittance

A coating film was formed on the silicon substrate in the same manner as in the evaluation of the radiation sensitivity. This silicon substrate was heated in a clean oven at 220 DEG C for 1 hour to obtain a cured film. The light transmittance at a wavelength of 400 nm was measured by using a spectrophotometer (150-20 type double beam (Hitachi SEISAKUSHO Co., Ltd.)). In this case, transparency is poor when the content is less than 90%, and transparency is good when the content is 90% or more. The evaluation results are shown in Table 1.

(4) Voltage Conservation Rate

The prepared liquid composition was spin-coated on a soda glass substrate on which an SiO ₂ film was formed to prevent elution of sodium ions on the surface and further an ITO (indium-tin oxide alloy) electrode was deposited in a predetermined shape, In a clean oven for 10 minutes to form a coating film having a thickness of 2.0 탆.

Subsequently, the coating film was exposed at an exposure amount of 500 J / m &lt; 2 &gt; without interposing a photomask. Thereafter, this substrate was immersed in a developer consisting of 0.04 mass% potassium hydroxide aqueous solution at 23 占 폚 for 1 minute, developed, washed with ultrapure water and air-dried, and post baked at 230 占 폚 for 30 minutes to cure the coating film To form a cured 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 sealant mixed with 0.8 mm glass beads, and then a liquid crystal MLC6608 (trade name) manufactured by Merck Ltd. was injected, .

Subsequently, the liquid crystal cell was placed in a thermostatic chamber at 60 DEG C, and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage maintaining ratio measurement system "VHR-1A type" (trade name) manufactured by Toyobo Co., Ltd. The applied voltage at this time is a square wave of 5.5 V, and the measurement frequency is 60 Hz. Here, the voltage holding ratio is a value of a voltage applied to the liquid crystal cell after 16.7 milliseconds / 0 milliseconds. If the voltage holding ratio of the liquid crystal cell is 90% or less, it means that 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. high.

As is clear from the results in Table 1, the positive radiation-sensitive compositions of Examples 1 to 10 including the components [A], [B] and [C] Sensitive positive radiation sensitive composition of the present invention exhibited excellent shape stability of the contact hole and had high developing property and pattern forming property. It was also found that each of the positive-tone radiation-sensitive compositions of the Examples can form an interlayer insulating film which satisfies generally required characteristics of radiation sensitivity, light transmittance and voltage holding ratio.

As described above, the positive radiation-sensitive composition of the present invention has excellent radiation sensitivity, and the obtained interlayer insulating film has a high light transmittance and a high voltage holding ratio, and has excellent developability capable of coping with changes in the conditions for forming a cured film and And has a pattern forming property. Accordingly, the positive-tone radiation-sensitive composition is suitably used for forming an interlayer insulating film or the like of a display element.

1: substrate
2:
3: Contact hole

Claims (6)

[A] a polymer having a structural unit containing a group represented by the following formula (1) and an epoxy group-containing structural unit in the same or different polymer molecules,
[B] the photoacid generator, and
[C] a compound represented by the following formula (2)
A positive radiation-sensitive composition comprising:

(1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and a part or all of the hydrogen atoms of the alkyl group, cycloalkyl group or aryl group is substituted with a substituent R ³ represents an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, or a group represented by -M (R ^3m ) ₃ (wherein M represents Si, Ge (in which R ¹ and R ² are not hydrogen atoms) Or Sn and R ^3m is an alkyl group), some or all of these hydrogen atoms may be substituted with a substituent, and R ¹ and R ³ may be connected to form a cyclic ether structure);

(2), X is a divalent straight-chain aliphatic hydrocarbon group having 6 to 20 carbon atoms, Y ¹ and Y ² are each independently a single bond, an ester bond, an amide bond or a urethane bond, R ⁴ and R ⁵ are, each independently, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, sulfo, sulfonyl group, or the formula (i) ~ a group represented by any of (vi); However, Y ¹ or Y ² is unity coalescence When R ⁴ or R ⁵ connected to Y ¹ or Y ² is not an alkyl group having 1 to 6 carbon atoms);

Wherein R ⁶ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁷ is a hydrogen atom or a methyl group, m is an integer of 0 to 6, provided that in the formula (2) of Y ¹ or Y ² when the sum is unity, m in R ⁴ or R ⁵ that is connected with a Y ¹ or Y ² is zero). The method according to claim 1,
(I), (ii), (iii) and (vi), at least one of R ⁴ and R ⁵ of the compound represented by the formula (2) Composition. The method according to claim 1,
[B] A positive radiation-sensitive composition having an oxime sulfonate group represented by the following formula (3) as a photoacid generator.

(In the formula (3), R ^B1 is a linear or branched alkyl group, a cycloalkyl group or an aryl group, and some or all of the hydrogen atoms of these groups may be substituted with a substituent). The method according to any one of claims 1, 2, and 3,
A positive radiation-sensitive composition for use in forming an interlayer insulating film of a display element. (1) a step of forming a coating film of the positive radiation-sensitive composition described in (4) above on a substrate,
(2) a step of irradiating at least a part of the coating film formed in the step (1)
(3) a step of developing the coated film irradiated with the radiation in the step (2)
(4) a step of heating the developed coating film in the step (3)
Of the interlayer insulating film of the display element. An interlayer insulating film of a display element formed from the positive radiation-sensitive composition of claim 4.

Images