KR101430506B1 - Positive radiation-sensitive composition for discharge nozzle coating method, interlayer insulating film for display element, and formation method for same - Google Patents

Abstract

(A) a polymer having a structural unit (I) containing a group represented by the following formula (1) and an epoxy group-containing structural unit in the same or different polymer molecules, [B] an oxime sulfonate compound and an onium salt compound And [C] an organic solvent, and has a solid content concentration of 10 mass% or more and 30 mass% or less, a viscosity at 25 占 폚 of 2.0 mPa 占 퐏 or more and 12 mPa 占 퐏 or less , And (C) an organic solvent, at least (C1) an organic solvent having a vapor pressure at 20 ° C of from 0.1 mmHg or more to less than 1 mmHg, which is a positive radiation-sensitive composition for a discharge nozzle coating method.

Description

TECHNICAL FIELD [0001] The present invention relates to a positive radiation-sensitive composition for a discharge nozzle type coating method, an interlayer insulating film for a display element, and a method for forming the same. BACKGROUND ART [0002]

The present invention relates to a positive radiation-sensitive composition for a discharge nozzle type coating method suitable as a material for forming an interlayer insulating film for a display element such as a liquid crystal display element or an organic EL display element, an interlayer insulating film for a display element formed by the composition, .

In the display element, an interlayer insulating film for a display element is formed for the purpose of insulating between wirings arranged in a generally layered form. As a material for forming a display element interlayer insulating film, a positive radiation sensitive composition is widely used because it requires few steps for obtaining a required pattern shape and also requires a high degree of flatness in the obtained interlayer insulating film for a display element.

With respect to such a positive radiation-sensitive composition, JP-A-2004-264623 proposes a positive radiation-sensitive resin composition containing a resin containing an acetal structure and / or a ketal structure and an epoxy group and an acid generator have. However, this positive radiation-sensitive resin composition has insufficient radiation sensitivity and is not satisfactory as a material for forming an interlayer insulating film for a display element.

On the other hand, Japanese Patent Laid-Open No. 2002-131896 discloses a spin coating method as a method of applying a radiation-sensitive composition to a small substrate. According to this spin coating method, good application uniformity can be obtained as a coating method in which a radiation-sensitive composition is dropped onto the center of a substrate and then the substrate is spun. However, when this spin coating method is applied to a large-sized substrate, it is necessary to secure a sufficient tact time because of the fact that a large number of radiation sensitive compositions are discarded by spinning, cracks in the substrate due to high- And the like. In addition, when applied to a substrate of a larger size, a special motor is required to obtain acceleration required for spinning, which is disadvantageous in terms of manufacturing cost.

Thus, as a coating method instead of the spin coating method, a discharge nozzle type coating method in which a radiation-sensitive composition is discharged from a nozzle and is coated on a substrate is employed. The ejection nozzle type coating method is a coating method for forming a coating film on a substrate by sweeping the coating nozzle in a predetermined direction. It is possible to reduce the amount of the radiation sensitive composition required for coating as compared with the spin coating method, Which is also advantageous in terms of manufacturing cost. However, when the conventional radiation sensitive composition is applied by the discharge nozzle coating method, coating unevenness may occur, which hinders realization of a high degree of flatness required as a characteristic of the display element interlayer insulating film have. For example, Japanese Laid-Open Patent Publication No. 2009-98673 discloses that the radiation sensitive composition described in this publication can be applied by a method other than the spin coating method, but a suitable viscosity, solid concentration, It is not disclosed specifically, and in the examples, coating by the discharge nozzle type coating method is not applied.

In view of this situation, it is possible to form an interlayer insulating film for a display element having a high radiation sensitivity and a high degree of flatness (uniformity in film thickness) without coating unevenness, and furthermore, Development of a positive radiation-sensitive composition has been desired.

Japanese Patent Application Laid-Open No. 2004-264623 Japanese Patent Application Laid-Open No. 2002-131896 Japanese Laid-Open Patent Publication No. 2009-98673

The present invention has been made based on the above-described circumstances, and it is an object of the present invention to provide a display element interlayer insulating film having a high radiation sensitivity and a high degree of flatness (uniformity in film thickness) A positive radiation-sensitive composition for a discharge nozzle type coating method, an interlayer insulating film for a display element, and a method of forming the same.

According to an aspect of the present invention,

[A] A polymer having a structural unit (I) 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) a compound selected from the group consisting of an oxime sulfonate compound and an onium salt compound (hereinafter also referred to as "[B] compound"), and

[C] Organic solvent

, The solid content concentration is 10 mass% or more and 30 mass% or less, the viscosity at 25 占 폚 is 2.0 mPa 占 퐏 or more and 12 mPa 占 퐏 or less,

(C) a positive radiation-sensitive composition for an ejection-nozzle-type coating method comprising an organic solvent at least (C1) an organic solvent having a vapor pressure at 20 ° C of from 0.1 mmHg or more to less than 1 mmHg;

(In the formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, with the proviso that some or all of the hydrogen atoms of the alkyl group, cycloalkyl group and aryl group are substituted even good; also, R ¹ and R ² both are not a hydrogen atom; R ³ is an alkyl group, cycloalkyl group, aralkyl group, aryl group, or -M (R ^3m) group represented by _3; however, these groups M is Si, Ge or Sn; R ^3m is an alkyl group, with the proviso that R ¹ and R ³ are linked together with the carbon atoms to which they are bonded, It may form a cyclic ether).

This composition has a high radiation sensitivity at the time of exposure in that it contains the [A] polymer, the [B] compound and the [C] organic solvent. By setting the solid content concentration of the composition to the above-specified range, it is possible to effectively suppress the occurrence of coating unevenness. Further, by setting the viscosity of the composition to the above-specified range, even if coating unevenness occurs, It is possible to achieve a high degree of uniformity in viscosity and to realize high-speed coating performance. Further, by using the [C] organic solvent having the vapor pressure in the above specific range, even if the discharge nozzle type coating method is employed, high-speed coating can be performed while preventing coating unevenness.

(C2) an organic solvent, wherein the content of the organic solvent is (C1) an organic solvent and ((C2) an organic solvent having a vapor pressure of not less than 1 mmHg and not more than 20 mmHg at 20 DEG C) (C2) the content of the organic solvent is 10 mass% or more and 50 mass% or more with respect to the total amount of the organic solvent (C1) and the organic solvent (C2) % Or less. When the mass ratio of the organic solvent having a low vapor pressure (C1) to the organic solvent having a high vapor pressure (C2) is set to the above specific range, the residual solvent amount in the coated film after the prebaking, in particular, is optimized and the fluidity of the coating film is balanced As a result, it is possible to suppress the occurrence of coating unevenness (uneven streaks, uneven pin marks, fog unevenness, etc.) and to further improve film thickness uniformity. In addition, the amount of acid generated and the acid-dissociable group are highly balanced by optimizing the amount of residual solvent, so that the radiation sensitivity tends to be better.

The composition further contains at least one surfactant (hereinafter also referred to as "[D] surfactant") selected from the group consisting of [D] a fluorine surfactant or a silicone surfactant, It is preferable that the content of the activator is 0.01 parts by mass or more and 2 parts by mass or less based on 100 parts by mass of the polymer [A]. By further containing the [D] surfactant in the composition, the surface smoothness of the coating film can be improved, and as a result, the uniformity of film thickness of the formed interlayer insulating film for a display element can be further improved. Further, by setting the content of the [D] surfactant to the above specific range, the surface smoothness of the coating film can be further improved.

In the composition, it is preferable to further contain the [E] polyfunctional (meth) acrylate compound. By further containing the [E] polyfunctional (meth) acrylate compound in the composition, transmittance and heat-resistant transparency of the display element interlayer insulating film can be improved.

In the composition, it is preferable to further contain [F] antioxidant. By further containing the [F] antioxidant in the composition, transmittance and heat-resistant transparency of the interlayer insulating film for a display element can be improved.

In this composition, it is preferable to further contain a [G] epoxy compound. By further containing the [G] epoxy compound in the composition, the transmittance and the heat-resistant transparency of the interlayer insulating film for a display element can be improved.

(C1) The organic solvent is at least one organic solvent selected from the group consisting of diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, benzyl alcohol and dipropylene glycol monomethyl ether (C 2) organic solvent is selected from the group consisting of diethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, propylene glycol monomethyl ether acetate, cyclohexanone, acetic acid n -Butyl, methyl isobutyl ketone, and methyl 3-methoxypropionate is preferable. By selecting the (C1) organic solvent and the (C2) organic solvent from the above specific compounds, occurrence of coating unevenness can be further suppressed and film thickness uniformity can be further improved.

The present invention suitably includes an interlayer insulating film for a display element formed from the composition.

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

(1) a step of applying the composition to a substrate while relatively moving the ejection nozzle and the substrate to form a coating film,

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

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

(4) heating the developed coating film.

According to the forming method, the composition capable of forming a display element interlayer insulating film having high radiation sensitivity and excellent film thickness uniformity as well as being capable of high-speed coating can be used for exposure, development, and heating using radiation- It is possible to form an interlayer insulating film for a display element having a fine and precise pattern easily. Further, the display element interlayer insulating film thus formed has no coating unevenness and has a high degree of flatness, and can be suitably used for a display element such as a liquid crystal display element or an organic EL display element.

The term " ejection nozzle type coating method " used herein means a method of ejecting and applying the composition onto a substrate (nozzle) through a nozzle. For example, a plurality of nozzle holes may be formed in a column shape , A method of applying the composition using a nozzle having a discharge port arranged in a slit-shaped discharge port, a method of applying the composition using a nozzle having a slit-shaped discharge port, and the like. After coating the composition on a substrate, And an operation of adjusting the film thickness by spinning. The polymer [A] referred to in the present specification is a concept including a case in which a structural unit (I) is contained in one polymer molecule and an epoxy group-containing structural unit is contained in a polymer molecule different from the one polymer molecule. As used herein, the term " radiation " in the " radiation-sensitive resin composition " is a concept including visible light, ultraviolet light, far ultraviolet light, X-ray and charged particle light.

INDUSTRIAL APPLICABILITY As described above, the positive-tone radiation-sensitive composition for a discharge nozzle coating method of the present invention has a high radiation sensitivity and a high flatness (film thickness uniformity) without coating unevenness, And high-speed coating can be performed. Therefore, the composition is suitable as a material for forming an interlayer insulating film for a display element such as a liquid crystal display element or an organic EL display element.

(Mode for carrying out the invention)

The positive radiation-sensitive composition for a dispensing nozzle coating method of the present invention contains a polymer [A], a [B] compound and an organic solvent [C]. The composition may also contain, as a suitable component, a [D] surfactant, a [E] polyfunctional (meth) acrylate compound, an [F] antioxidant and a [G] epoxy compound. In addition, as long as the effect of the present invention is not impaired, other optional components may be contained. Hereinafter, each component will be described in detail.

<[A] Polymer>

The polymer [A] has structural units (I) and epoxy group-containing structural units in the same or different polymer molecules, and may have other structural units as required. The embodiment of the polymer [A] having the structural unit (I) and the epoxy group-containing structural unit is not particularly limited,

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

(Ii) a polymer having a structural unit (I) in one polymer molecule and an epoxy group-containing structural unit in a different polymer molecule; [A] when two polymer molecules are present in the polymer;

(Iii) a polymer having a structural unit (I) and an epoxy group-containing structural unit in one polymer molecule and a structural unit (I) in a polymer molecule different from the structural unit , [A] when three kinds of polymer molecules are present in the polymer;

(Iv) a case in which, in addition to the polymer molecules defined in (i) to (iii), one or more other polymer molecules are contained in the polymer [A].

[Structural unit (I)]

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

In the formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. However, some or all of the hydrogen atoms of the alkyl group, cycloalkyl group and aryl group may be substituted. In addition, R ¹ and R ² are not both hydrogen atoms. R ³ is an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group or a group represented by -M (R ^3m ) ₃ . However, some or all of the hydrogen atoms of these groups may be substituted. M is Si, Ge or Sn; R ^3m is an alkyl group. R ¹ and R ³ may be connected to form a cyclic ether together with the carbon atom to which they are bonded.

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

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

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

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

As examples of the alkyl group, cycloalkyl group and aryl group represented by R ³ , for example, the groups exemplified as R ¹ and R ^{2 described} above can be applied. Examples of the aralkyl group represented by R ³ include aralkyl groups having 7 to 20 carbon atoms such as a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group. Examples of -M (R ^3m) ₃ represented by the above R ^3, for example, and the like trimethylsilanyl group, a trimethyl-germyl. As the substituent of the aralkyl group represented by R ³ or -M (R ^3m ) _3, the substituents exemplified for R ¹ and R ² above may be applied.

Examples of the cyclic ether which may be formed together with the carbon atom to which R ¹ and R ³ are connected and to which they are bonded include 2-oxetanyl group, 2-tetrahydrofuranyl group, 2-tetrahydropyranyl group, Nylon and the like.

The structural unit (I) may have an acetal structure or a ketal structure by having a functional group which is bonded to another carbon atom to have an acetal structure or a ketal structure.

Examples of the functional group that is bonded to the other carbon atom to have an acetal structure include 1-methoxyethoxy group, 1-ethoxyethoxy group, 1-n-propoxyethoxy group, 1- Butoxyethoxy group, 1-t-butoxyethoxy group, 1-cyclopentyloxyethoxy group, 1-n-butoxyethoxy group, 1-cyclohexyloxyethoxy group, 1-norbornyloxyethoxy group, 1-boronyloxyethoxy group, 1-phenyloxyethoxy group, 1- (1-naphthyloxy) ethoxy group (Cyclohexyl) (n-propoxy) methoxy group, (cyclohexyl) (n-propoxy) (Cyclohexyl) (phenoxy) methoxy group, (cyclohexyl) (cyclohexyloxy) methoxy group, (cyclohexyl) (phenoxy) , (Phenyl) (methoxy) methoxy group, (phenyl) (ethoxy (Phenyl) (phenoxy) methoxy group, (phenyl) (n-propoxy) methoxy group, (Benzyl) (n-propoxy) methoxy group, (benzyl) (methoxy) methoxy group, (benzyl) (ethoxy) (Benzyl) (benzyloxy) methoxy group, 2-tetrahydrofuranyloxy group, 2-tetrahydropyranyloxy group, benzyloxy group, 1-trimethylsilanyloxyethoxy group, 1-trimethylgermyloxyethoxy group, and the like. Of these, preferred are 1-ethoxyethoxy group, 1-cyclohexyloxyethoxy group, 2-tetrahydrofuranyloxy group, 1-n-propoxyethoxy group, A tetrahydropyranyloxy group is preferred.

Methyl-1-methoxyethoxy group, 1-methyl-1-ethoxyethoxy group, 1-methyl-1-n Propoxyethoxy group, 1-methyl-1-i-butoxyethoxy group, 1-methyl-1-i-butoxyethoxy group, 1 Methyl-1-cyclopentyloxyethoxy group, 1-methyl-1-cyclohexyloxy group, 1-methyl-1-cyclopentyloxyethoxy group, Methyl-1-norbornyloxyethoxy group, 1-methyl-1-bornyloxyethoxy group, 1-methyl- Methyl-1-benzyloxyethoxy group, 1-ethyl-1-methoxyethoxy group, 1-ethyl-1-pentyloxyethoxy group, 1-i-propoxyethoxy group, 1-ethyl-1-n-butoxyethoxy group, 1-ethyl-1-n-butoxyethoxy group, -Ethyl-1-i-butoxyethoxy group, 1-ethyl-1-sec-butoxyethoxy 1-cyclohexyloxyethoxy group, 1-ethyl-1-t-butoxyethoxy group, 1-ethyl-1-cyclopentyloxyethoxy group, Ethyl-1-phenyloxyethoxy group, 1-ethyl-1- (1-naphthyloxy) ethoxy group, 1-ethyl 1-cyclohexyl-1-methoxyethoxy group, 1-cyclohexyl-1-ethoxyethoxy group, 1- 1-cyclohexyl-1-phenoxyethoxy group, 1-cyclohexyl-1-i-propoxyethoxy group, 1-cyclohexyl-1-cyclohexyloxyethoxy group, Phenyl-1-ethoxyethoxy group, a 1-phenyl-1-n-propyloxy group, a 1-phenyl-1-butoxyethoxy group, Phenyl-1-cyclohexyloxyethoxy group, a 1-phenyl-1-phenyloxyethoxy group, a 1-phenyl-1-i-propoxyethoxy group, Benzyloxyethoxy Benzyl-1-i-propoxyethoxy group, 1-benzyl-1-i-propoxyethoxy group, 1-cyclohexyloxyethoxy group, 1-benzyl-1-phenyloxyethoxy group, 1-benzyl-1-benzyloxyethoxy group, 2- (2-methyl-tetrahydrofura (2-methyl-tetrahydropyranyl) oxy group, 1-methoxy-cyclopentyloxy group, 1-methoxy-cyclohexyloxy group and the like. Of these, 1-methyl-1-methoxyethoxy group and 1-methyl-1-cyclohexyloxyethoxy group are preferable.

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

In the formulas (1-1) to (1-3), R ¹ , R ² and R ³ have the same meanings as in the formula (1). In the formulas (1-1) and (1-3), R 'is a hydrogen atom or a methyl group.

Examples of the monomer giving the structural unit represented by the above formulas (1-1) to (1-3) (hereinafter also referred to as "acetal structure-containing monomer") include,

(Meth) acrylic acid 1- (cycloalkyloxy) alkyl, 1- (haloalkoxy) alkyl (meth) acrylate, 1- (aralkyloxy) (Meth) acrylate-based acetal structure-containing monomers such as tetrahydropyranyl acrylate and tetrahydropyranyl 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.

More specific examples of the (meth) acrylate-based acetal structure-containing monomer include 1-ethoxyethyl methacrylate, 1-methoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, Methoxyethyl methacrylate, 1-t-butoxyethyl methacrylate, 1- (2-chloroethoxy) ethyl methacrylate, 1- (2-ethylhexyloxy) 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-chloroethoxy) acrylic acid ) Ethyl acrylate, 1- (2-ethylhexyloxy) ethyl acrylate, 1-n-propoxyethyl acrylate, 1-cyclohexyloxyethyl acrylate, 1- Cyclohexylethoxy) ethyl, 1-benzyloxyethyl acrylate, 2-tetrahydropyranyl acrylate, and the like.

More specific examples of the norbornene acetal structure-containing monomer include 2,3-di (1- (trimethylsilanyloxy) ethoxy) carbonyl) -5-norbornene, 2,3-di 5-norbornene, 2,3-di (1-methoxyethoxycarbonyl) -5-norbornene, (Cyclohexyloxy) ethoxycarbonyl) -5-norbornene, 2,3-di (1- (benzyloxy) ethoxycarbonyl) -5-norbornene and the like.

More specific examples of the styrenic acetal structure-containing monomer include p or m-1-ethoxyethoxystyrene, p or m-1-methoxyethoxystyrene, p or m-1-n- P or m-1- (2-chloroethoxy) ethoxystyrene, p or m-1-isobutoxyethoxystyrene, p or m-1- (1,1-dimethylethoxy) p or m-1-cyclohexyloxyethoxystyrene, p or m-1-n-propoxyethoxystyrene, p or m- 1- (2-cyclohexylethoxy) ethoxystyrene, p or m-1-benzyloxyethoxystyrene, and the like.

As the structural unit (I), a structural unit represented by the above formula (1-1) is preferable. Examples of the acetal structure-containing monomer include (meth) acrylic acid 1-alkoxyalkyl, (meth) acrylate tetrahydropyranyl, (meth) acrylic acid 1-alkoxyalkoxystyrene and tetrahydropyranyloxystyrene, Alkoxyalkyl is more preferable, and 1-ethoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 2-tetrahydropyranyl methacrylate and 1-benzyloxyethyl methacrylate are particularly preferable.

As the acetal structure-containing monomer, a commercially available product may be used, or a product synthesized by a known method may be used. For example, the acetal structure-containing monomer imparting the structural unit represented by the above formula (1-1) can be produced, for example, by a method in which (meth) acrylic acid is reacted with a vinyl ether in the presence of an acid catalyst Can be synthesized.

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

The polymer [A] may contain one or more structural units (I). The content of the structural unit (I) in the polymer [A] is not particularly limited as long as the polymer [A] exhibits alkali solubility by the acid and exhibits the desired heat resistance of the interlayer insulating film for a display element, When the molecule contains both the structural unit (I) and the epoxy group-containing structural unit, it is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, and still more preferably 20% % By mass is particularly preferable.

On the other hand, when one polymer molecule has a structural unit (I) and the other polymer molecule has an epoxy group-containing structural unit, the ratio of the structural unit (I) in one polymer molecule having the structural unit The content is preferably 40% by mass to 99% by mass, more preferably 50% by mass to 98% by mass, and particularly preferably 55% by mass to 95% by mass,

[Epoxy group-containing structural unit]

[A] The polymer has an epoxy group-containing structural unit together with the structural unit (I). The epoxy group-containing structural unit is a structural unit derived from an epoxy group-containing monomer. Also, the epoxy group is a concept including an oxiranyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure). By having the polymer [A] having the epoxy group-containing structural unit in the molecule, the hardness of the display element interlayer insulating film obtained from the composition can be improved and the heat resistance can be further improved.

Examples of the epoxy group-containing monomer which imparts an epoxy group-containing structural unit include

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

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

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

3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) 3-methyloxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) 3-ethyloxetane, 3- (2-acryloyloxyethyl) -3-phenyloxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl 3-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) 2- (acryloyloxymethyl) -2-methyloxetane, 2- (acryloyloxymethyl) -3-phenyloxetane, 2- ) -2-ethyloxetane, 2- (acryloyloxymethyl) -2- (2-acryloyloxyethyl) -2-ethyl (2-acryloyloxyethyl) oxetane, 2- Oxetane, 2- (2-acryloyloxyethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) -2-ethyloxetane, 2- (methacryloyloxymethyl) -2-phenyloxetane, 2- (2-methacryloyloxyethyl) oxetane, 2- 2- (2-methacryloyloxyethyl) -2-methyloxetane, 2- (2-methacryloyloxyethyl) -2-ethyloxetane, 2- (Meth) acrylic compounds containing an oxetanyl group such as 2-phenyloxetane.

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

The polymer [A] may have one or more epoxy group-containing structural units. 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 display element interlayer insulating film is exhibited, and the structural unit (I) and the epoxy group- Is preferably from 1% by mass to 60% by mass, more preferably from 15% by mass to 55% by mass, more preferably from 20% by mass to 50% by mass, based on the structural unit (I) contained in the polymer [A] % Is particularly preferable.

On the other hand, when one polymer molecule has a structural unit (I) and another polymer molecule has an epoxy group-containing structural unit, the content of the epoxy group-containing structural unit contained in one polymer molecule having an epoxy group- By mass, preferably from 1% by mass to 80% by mass, more preferably from 30% by mass to 70% by mass, and particularly preferably from 35% by mass to 65% by mass,

[Other structural units]

The polymer [A] may contain other structural units other than the structural unit (I) and the epoxy group-containing structural unit. Examples of the monomer giving another structural unit include a monomer having a carboxyl group or a derivative thereof, a monomer having a hydroxyl group, and other monomers.

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

Examples of the monomer having a hydroxyl group include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and 4-hydroxymethylcyclohexylmethyl acrylate; 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl methacrylate, 4- And hydroxyalkyl methacrylate such as hydroxymethyl-cyclohexylmethyl. From the viewpoint of the heat resistance of the resulting interlayer insulating film for a display element, among the monomers having a hydroxyl group, it is preferable to use at least one monomer selected from the group consisting of 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxymethyl-cyclohexylmethyl acrylate, 4-hydroxymethyl-cyclohexylmethyl methacrylate are preferred.

As other monomers, for example,

Alkyl acrylates such as methyl acrylate and i-propyl acrylate;

Methyl methacrylate such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, and t-butyl methacrylate;

2-methylcyclohexyl acrylate, 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) ethyl , Acrylic acid alicyclic alkyls such as isobornyl acrylate;

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

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

Aralkyl of methacrylic acid such as phenyl methacrylate or benzyl methacrylate, or aralkyl of methacrylic acid;

Dialkyl dicarboxylates such as diethyl maleate, diethyl fumarate and diethyl itaconate;

Unsaturated heterocyclic 5-membered methacrylic acid esters or unsaturated heterocyclic 6-membered methacrylic acid containing 1 oxygen atom such as tetrahydrofuranyl methacrylate, tetrahydrofuryl methacrylate, and tetrahydropyran-2-methyl methacrylate;

4-methacryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methacryloyloxymethyl- , 4-methacryloyloxymethyl-2-cyclohexyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl- Unsaturated heterocyclic 5-membered cyclic methacrylic acid containing two oxygen atoms such as methacryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane;

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 acrylic acid 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- N-substituted maleimides such as 6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate and N- (9-acridinyl) maleimide;

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

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

Among these 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, benzyl methacrylate, the above carboxyl group or a derivative thereof From the viewpoint of copolymerization reactivity with monomers, monomers having hydroxyl groups, and developability of the composition.

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

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

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

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

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

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

Mobile phase: tetrahydrofuran

Column temperature: 40 DEG C

Flow rate: 1.0 mL / min

Sample concentration: 1.0 mass%

Sample injection amount: 100 μL

Detector: differential refractometer

Standard material: monodisperse polystyrene

<Method of synthesizing [A] polymer>

The polymer [A] can be synthesized by radical copolymerization of the monomers imparting the respective structural units. In the case of synthesizing the polymer [A] containing both the structural unit (I) and the epoxy group-containing structural unit in the same polymer molecule, a copolymer containing at least an acetal structure-containing monomer and an epoxy group-containing monomer may be copolymerized. On the other hand, in the case of synthesizing a polymer [A] having a structural unit (I) 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 (I), and at least a polymerizable solution containing at least an epoxy group-containing monomer is subjected to radical polymerization 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 of the polymer [A] include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, Propylene glycol monoalkyl ether propionate, aromatic hydrocarbons, ketones, and other esters.

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

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

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

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

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

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

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

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

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

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

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

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 acetate, propylene glycol monomethyl ether and butyl methoxyacetate are more preferred.

As the polymerization initiator used in the polymerization reaction, those known as radical polymerization initiators can be used. For example,

Azobis- (2,4-dimethylvaleronitrile) (ADVN), 2,2'-azobis- (4-methoxy-2,2'-azobisisobutyronitrile, 4-dimethylvaleronitrile), and 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 and the like.

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

&Lt; [B] Compound &gt;

The [B] compound is at least one compound selected from the group consisting of an oxime sulfonate compound and an onium salt compound, and is a compound which generates an acid upon irradiation with radiation. As the radiation, visible rays, ultraviolet rays, far ultraviolet rays, electron rays, X rays, and the like can be used. When the composition contains a [B] compound and a polymer [A] having an acid-dissociable group, a positive radiation-sensitive property can be exhibited.

[Oxime sulfonate compound]

Examples of the oxime sulfonate compound include compounds containing an oxime sulfonate group represented by the following formula (2).

In the above formula (2), R ^B1 is a linear, branched, cyclic alkyl group which may be substituted, or an aryl group which may be substituted.

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

Examples of the oxime sulfonate group-containing compound represented by the above formula (2) include oxime sulfonate compounds represented by the following formula (3).

In the formula (3), R ^B1 has the same meaning as in the formula (2). X is an alkyl group, an alkoxy group, or a halogen atom. m is an integer of 0 to 3; Provided that when plural Xs are present, plural Xs may be the same or different.

The alkyl group which may be represented by X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group represented by X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom represented by X is preferably a chlorine atom or a fluorine atom. As m, 0 or 1 is preferable. In the above formula (3), a compound wherein m is 1, X is a methyl group, and X is an ortho substituted position is preferable.

Examples of the oxime sulfonate compound represented by the above-mentioned (3) include compounds represented by the following formulas (i) to (v), respectively.

Also, the compound (i) (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile, the compound (ii) (5-octylsulfonyloxyimino- Thiophen-2-ylidene) - (2-methylphenyl) acetonitrile, compound (iii) (camphorsulfonyloxyimino-5H- (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile and the compound (v) (5-octylsulfonyloxyimino) - (4- Phenyl) acetonitrile is commercially available.

[Onium salts]

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

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

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

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

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

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

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

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

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

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

The [B] compound may also include a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonic acid ester compound, a carbonic acid ester compound and the like.

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

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

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

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

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

As the oxime sulfonate compound, a compound containing an oxime sulfonate group represented by the above formula (2) is preferable, an oxime sulfonate compound represented by the above formula (3) is more preferable, (2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene) - ) Acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile, (camphorsulfonyloxyimino-5H-thiophen- ) - (2-methylphenyl) acetonitrile, and (5-octylsulfonyloxyimino) - (4-methoxyphenyl) acetonitrile. As the onium salts, tetrahydrothiophenium salts and benzylsulfonium salts are preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, benzyl-4-hydroxy Phenylmethylsulfonium hexafluorophosphate is more preferable.

The [B] compounds may be used alone or in combination of two or more. The content of the [B] compound 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, relative to 100 parts by mass of the polymer [A]. By setting the content of the [B] compound within the above-specified range, the radiation sensitivity of the composition can be optimized to form an interlayer insulating film for a display device having high surface hardness while maintaining transparency.

<[C] Organic solvent>

The composition is prepared by dissolving or dispersing the [C] organic solvent by mixing a suitable component such as the [A] polymer, the [B] compound and, if necessary, the [D] surfactant, and other optional components. [C] As the organic solvent, at least (C1) an organic solvent having a vapor pressure at 20 ° C of 0.1 mmHg or more and less than 1 mmHg is contained. The organic solvent (C2) preferably contains an organic solvent having a vapor pressure at 20 DEG C of 1 mmHg or more and 20 mmHg or less. By using the [C] organic solvent having the vapor pressure in the above specific range, even if a discharge nozzle type coating method is employed, high-speed coating can be performed while preventing coating unevenness. The vapor pressure can be measured by a known method, but in this specification refers to a value measured by the transfer method (gas flow method).

As the [C] organic solvent, those that do not react with each component are suitably used so that each component is uniformly dissolved or dispersed. Examples of the organic solvent [C] include benzyl alcohol, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, diethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, Diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, lactic acid esters, aliphatic carboxylic acid esters, amides, ketones, . These may be used alone or in combination of two or more.

As the organic solvent (C1), for example,

Benzyl alcohol;

Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether;

Ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and ethylene glycol dipropyl ether;

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether;

Diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether;

Diethylene glycol dialkyl ethers such as diethylene glycol diethyl ether and diethylene glycol ethyl methyl ether;

Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate and diethylene glycol monobutyl ether acetate;

Dipropylene glycol monoalkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether;

Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether;

Dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate and dipropylene glycol monobutyl ether acetate;

Lactic acid esters such as n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, and isoamyl lactate;

Ethyl acetate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 3-ethoxypropionate, ethyl 2-hydroxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl- Aliphatic carboxylic acid esters such as ethyl acetate, methyl pyruvate and ethyl pyruvate;

Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide and N, N-dimethylacetamide;

And ketones such as N-methylpyrrolidone and? -Butyrolactone.

The organic solvent (C1) may be used alone or in combination of two or more. The organic solvent (C1) is at least one organic solvent selected from the group consisting of diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, benzyl alcohol and dipropylene glycol monomethyl ether desirable.

Examples of the organic solvent (C2) include diethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate , Cyclohexanone, ethyl acetate, propyl acetate, n-butyl acetate, methylpropyl ketone, methyl isobutyl ketone, methyl 3-methoxypropionate, methyl lactate, and ethyl lactate.

The organic solvent (C2) may be used alone or in combination of two or more kinds. Examples of the organic solvent (C2) include diethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, propylene glycol monomethyl ether acetate, cyclohexanone, n-butyl acetate, At least one organic solvent selected from the group consisting of methyl isobutyl ketone and methyl 3-methoxypropionate is preferable.

(C1) organic solvent and (C2) organic solvent are mixed, diethylene glycol ethyl methyl ether / diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether / propylene glycol monomethyl ether acetate, diethylene glycol ethyl methyl Ether / cyclohexanone, diethylene glycol diethyl ether / diethylene glycol dimethyl ether, diethylene glycol diethyl ether / propylene glycol monomethyl ether acetate, diethylene glycol diethyl ether / cyclohexanone, diethylene glycol diethyl ether / Methyl 3-methoxypropionate, diethylene glycol diethyl ether / methyl isobutyl ketone, diethylene glycol diethyl ether / n-butyl acetate is preferable.

The content of the (C2) organic solvent is preferably 10% by mass or more and 90% by mass or less, and more preferably 10% by mass or more and 50% by mass or less, based on the total amount of the organic solvent and the organic solvent. When the mass ratio of the organic solvent having a low vapor pressure (C1) to the organic solvent having a high vapor pressure (C2) is set to the above specific range, the residual solvent amount in the coated film after the prebaking, in particular, is optimized and the fluidity of the coating film is balanced As a result, it is possible to suppress the occurrence of coating unevenness (uneven streaks, uneven pin marks, fog unevenness, etc.) and further improve film thickness uniformity. Further, the amount of acid generated and the acid-dissociable group are highly balanced by optimizing the amount of residual solvent, and the radiation sensitivity tends to be good.

The solid content concentration of the composition is 10 mass% or more and 30 mass% or less. And preferably 20 mass% or more and 25 mass% or less. By setting the solid content concentration of the composition to the above specific range, it is possible to effectively suppress the occurrence of coating unevenness.

The viscosity of the composition at 25 캜 is 2.0 mPa · s or more and 12 mPa · s or less. It is preferably 2.0 mPa · s or more and 10 mPa · s or less. By setting the viscosity of the composition to the above-mentioned specific range, it is possible to achieve a balance in which the thickness uniformity can be maintained, even if coating unevenness occurs evenly, and a high-speed coating property can be realized.

&Lt; [D] Surfactant &gt;

The composition may further contain a [D] surfactant as a suitable component for further improving the film-forming property of the composition. Examples of the [D] surfactant include a fluorine-based surfactant and a silicone-based surfactant. By containing the [D] surfactant in the composition, the surface smoothness of the coating film can be improved, and the resulting film-thickness uniformity of the interlayer insulating film for a display element can be further improved.

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

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

Examples of the silicone surfactant include Toray silicone DC3PA, Copper DC7PA, Copper SH11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA, Copper SH-190, Copper SH-193, Copper SZ-6032, Copper TSF-4440, TSF-4445, TSF-4446, TSF-4460, TSF-4428, -4452 (manufactured by GE Toshiba Silicone), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[D] The surfactants may be used alone 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-specified range, the surface smoothness of the coating film can be further improved.

<[E] polyfunctional (meth) acrylate>

The composition may further contain [E] polyfunctional (meth) acrylate as a suitable component. By further containing the [E] polyfunctional (meth) acrylate compound in the composition, transmittance and heat-resistant transparency of the display element interlayer insulating film can be improved. Examples of the [E] polyfunctional (meth) acrylate include bifunctional (meth) acrylates and trifunctional or more (meth) acrylates.

Examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol di (meth) acrylate.

Examples of commercially available products of bifunctional (meth) acrylate include Aronix M-210, M-240, M-6200 (manufactured by TOAGOSEI Corporation), KAYARAD HDDA, -604 (manufactured by Nippon Kayaku), Viscoat 260, Copper 312, Copper 335HP (manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.), Wright acrylate 1,9-NDA .

Examples of the (meth) acrylate having three or more functional groups include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, Pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. (2-acryloyloxyethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate, succinic acid-modified penta (2-methacryloyloxyethyl) phosphate, dipentaerythritol hexamethacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, A straight chain alkylene group, and an alicyclic structure , And a polyfunctional urethane acrylate-based compound obtained by reacting a compound having at least two isocyanate groups, a compound having at least one hydroxyl group in the molecule and a compound having three to five (meth) acryloyloxy groups, etc. .

Examples of commercial products of trifunctional or more (meth) acrylates include Aronix M-309, M-400, M-405, M-450, M-7100, M- (Manufactured by Nippon Kayaku), TO-1450 (manufactured by TOAGOSEI), KAYARAD TMPTA, copper DPHA, copper DPCA-20, copper DPCA-30, copper DPCA-60, copper DPCA- ), Viscoat 295, Copper 300, Copper 360, Copper GPT, Copper 3PA, Copper 400 (manufactured by Osaka Yuki Kagakuko Co., Ltd.). Examples of commercially available products containing a polyfunctional urethane acrylate compound include New Frontier R-1150 (manufactured by Daiichi Kyo Seiyaku Co., Ltd.) and KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.).

Among these [E] polyfunctional (meth) acrylates, ethylene glycol di (meth) acrylate,? -Carboxypolycaprolactone monoacrylate, 1,9-nonanediol dimethacrylate, diethylene glycol dimethacrylate , Trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol A commercially available product containing a mixture of pentaacrylate and dipentaerythritol hexaacrylate, ethylene oxide-modified dipentaerythritol hexaacrylate, succinic acid-modified pentaerythritol triacrylate, and polyfunctional urethane acrylate-based compound is preferable.

[E] The polyfunctional (meth) acrylate may be used alone or in combination of two or more. The content of the [E] polyfunctional (meth) acrylate in the composition is preferably 1 part by mass to 30 parts by mass, more preferably 5 parts by mass to 15 parts by mass, per 100 parts by mass of the polymer [A] Wealth. By setting the content of the [E] polyfunctional (meth) acrylate within the above-specified range, the transmissivity and heat-resistant transparency of the interlayer insulating film for a display element can be further improved.

<[F] Antioxidant>

The composition may further contain [F] antioxidant as a suitable component. By further containing the [F] antioxidant in the composition, transmittance and heat-resistant transparency of the interlayer insulating film for a display element can be improved. [F] antioxidant in the present specification refers to a phenol compound, a compound having a hindered phenol structure, a compound having a hindered amine structure, a compound having an alkyl phosphate structure, and a compound having a thioether structure.

Examples of the phenol compound include 4-methoxyphenol and 4-ethoxyphenol.

Examples of the compound having a hindered phenol structure include 2,6-di-t-butyl-4-cresol, pentaerythritol tetrakis [3- (3,5- ) Propionate], thiodiethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5- Butylphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N'- Hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide), 3,3 ' -a, a ', a "- (methylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) (5-tert-butyl-4-hydroxy-m-tolyl) propionate, hexamethylenebis [3- (3,5-di butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert- Benzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -thione, 1,3,5-tris [ Methyl-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -thione, 2,6- Bis (octylthio) -1,3,5-triazin-2-ylamine) phenol and tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate. have.

Examples of commercial products of a compound having a hindered phenol structure include ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO- (Manufactured by Sumitomo Chemical Co., Ltd.), IRGANOX (manufactured by Sumitomo Chemical), AO-80, AO-330 (manufactured by ADEKA), sumilizerGM, copper GS, copper MDP-S, copper BBM-S, copper WX- (Manufactured by Chiba Japan), Yoshinox (manufactured by Chiba Japan), 1025, 1035, 1035, 1035, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, Yoshinox) BHT, copper BB, copper 2246G, copper 425, copper 250, copper 930, copper SS, copper TT, copper 917, copper 314 (manufactured by APIA CO., LTD.).

Examples of commercial products of the compound having a hindered amine structure include adecastab LA-52, LA-57, LA-62, LA-67, LA-63P, LA-68LD, LA- (Manufactured by Chiba Japan), LA-82, LA-87 (manufactured by ADEKA), sumilizer9A (manufactured by Sumitomo Chemical), CHIMASSORB119FL, copper 2020FDL, copper 944FDL, TINUVIN622LD, copper 144, copper 765, copper 770DF .

Examples of commercial products of the compounds having an alkyl phosphate structure include adecastab PEP-4C, copper PEP-8, copper PEP-8W, copper PEP-24G, copper PEP-36, copper HP-10, copper 2112, copper 260 , Copper 522A, Copper 1178, Copper 1500, Copper C, Copper 135A, Copper 3010, copper TPP (manufactured by ADEKA) and IRGAFOS 168 (manufactured by Ciba Japan).

Examples of commercial products of the compound having a thioether structure include adecastab AO-412S, AO-503 (manufactured by ADEKA), sumilizerTPL-R, copper TPM, copper TPS, copper TP- , IRGANOXPS800FD, and PS802FD (manufactured by Chiba Japan), DLTP, DSTP, DMTP, and DTTP (manufactured by APICA CORPORATION).

Among these [F] antioxidants, phenol compounds and compounds having a hindered phenol structure are preferable, and 4-methoxyphenol, 2,6-di-t-butyl-4-cresol, 1,3,5- (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2,4,6-tris , And pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate].

[F] The antioxidant may be used alone or in combination of two or more. The content of [F] antioxidant in the composition is preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.2 parts by mass to 5 parts by mass, based on 100 parts by mass of the polymer [A]. [F] By setting the content of the antioxidant within the above-specified range, the transmittance and heat-resistant transparency of the interlayer insulating film for a display element can be further improved.

<[G] Epoxy Compound>

The composition may further contain, as a suitable component, a compound further containing a compound having two or more epoxy groups in one molecule of [G]. By further containing the [G] epoxy compound in the composition, the transmittance and the heat-resistant transparency of the interlayer insulating film for a display element can be improved.

The [G] epoxy compound is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule, but the [A] polymer is excluded. Examples of the epoxy group include an oxiranyl group (1,2-epoxy structure), an oxetanyl group (1,3-epoxy structure) and 3,4-epoxycyclohexyl group.

As the compound having two or more oxiranyl groups in one molecule, for example,

Bisphenol A diglycidyl ether (polycondensation product of 4,4'-isopropylidenediphenol and 1-chloro-2,3-epoxypropane), bisphenol F diglycidyl ether, bisphenol S diglycidyl ether , Hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated Diglycidyl ether of a bisphenol compound such as bisphenol S diglycidyl ether;

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

Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin;

Phenol novolak type epoxy resins;

Cresol novolak type epoxy resin;

Polyphenol type epoxy resins;

Cyclic aliphatic epoxy resins;

Diglycidyl esters of aliphatic long chain dibasic acids;

Glycidyl esters of higher fatty acids;

Epoxidized soybean oil, and epoxidized linseed oil.

Examples of the compound having at least two oxetanyl groups (1,3-epoxy structures) in a molecule include 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis { Ethyl (3-oxetanyl)] methyl} ether, and the like.

Examples of the compound having two or more 3,4-epoxycyclohexyl groups in a molecule include 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 2- (3,4- Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis Epoxy-6-methylcyclohexanecarboxylate, methylene bis (3,4-epoxycyclohexane), dicyclopentane (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexanecarboxylate), lactone-modified 3,4-epoxycyclohexylmethyl-3 ', 4 '-Epoxy cyclohexanecarboxylate and the like.

As a commercially available product of the [G] epoxy compound, for example,

Epikote 1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 (manufactured by Japan Epoxy Resin Co., Ltd.) as the bisphenol A type epoxy resin;

As the bisphenol F type epoxy resin, Epikote 807 (manufactured by Japan Epoxy Resin Co., Ltd.) and the like;

As the phenol novolak type epoxy resin, Epicote 152, Copper 154, Copper 157S65 (manufactured by Japan Epoxy Resin Co., Ltd.), EPPN201, Copper 202 (manufactured by Nippon Kayaku Co., Ltd.) and the like;

EOCN102, Copper 103S, Copper 104S, Copper 1020, Copper 1025, Copper 1027 (manufactured by Nippon Kayaku Co., Ltd.), Epikote 180S75 (manufactured by Japan Epoxy Resin Co., Ltd.) and the like as cresol novolak type epoxy resin;

As the polyphenol type epoxy resin, Epikote 1032H60, XY-4000 (manufactured by Japan Epoxy Resin Co., Ltd.) and the like;

As the cyclic aliphatic epoxy resin, CY-175, 177, 179, Araldite CY-182, Copper 192 and Copper 184 (manufactured by Chiba Specialty Chemicals), ERL-4234, Copper 4299, (Manufactured by Dainippon Ink and Chemicals, Incorporated), Epicote 871, and Copper 872 (manufactured by Dainippon Ink and Chemicals, Inc.), Shodyne 509 (manufactured by Showa Denko K.K.), Epiclon 200 (Manufactured by Japan Epoxy Resin Co., Ltd.), ED-5661, Dong-5662 (manufactured by Celanese Coating Co., Ltd.);

As the aliphatic polyglycidyl ether, Epolight 100MF (manufactured by Kyoeisha Kagaku), Epiol TMP (manufactured by Nippon), 1,4-bis [(3-ethyl-3-oxetanylmethoxy ) Methyl] benzene, and bis {[1-ethyl (3-oxetanyl)] methyl} ether.

Of these, bisphenol A diglycidyl ether (polycondensation product of 4,4'-isopropylidenediphenol and 1-chloro-2,3-epoxypropane), bisphenol F diglycidyl ether, 1,4- Bis [(1-ethyl (3-oxetanyl)] methyl} ether, 3,4-epoxycyclohexylmethyl-3 ', 4' -Epoxy cyclohexanecarboxylate is preferred.

[G] epoxy compounds may be used alone or in combination of two or more. The content of the [G] epoxy compound in the composition is preferably 1 part by mass to 30 parts by mass, and more preferably 3 parts by mass to 15 parts by mass, relative to 100 parts by mass of the polymer [A]. By setting the content of the [G] epoxy compound within the above-specified range, the transmittance and heat-resistant transparency of the display element interlayer insulating film can be further improved.

&Lt; Other optional components &gt;

In addition to the above components [A] to [G], the composition of the present invention may further contain, if necessary, additives such as [H] adhesion aid, [I] basic compound, [J] quinone diazide compound May also be included. These other optional components may be used alone or in combination of two or more. Hereinafter, each component will be described in detail.

[[H] Adhesion preparation]

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

Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane,? - Glycidoxypropyltrimethoxysilane, gamma -glycidoxypropylalkyldialkoxysilane,? -Chloropropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyl tri Methoxysilane and the like. Among these,? -Glycidoxypropylalkyldialkoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane and? -Methacryloxypropyltrimethoxysilane are preferable.

The content of the [H] adhesion aid in the composition is preferably 0.5 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass or less, based on 100 parts by mass of the polymer [A]. [H] By setting the content of the adhesion aid within the above-specified range, adhesion between the display element interlayer insulating film and the substrate is further improved.

[[I] basic compound]

The basic compound [I] may be arbitrarily selected from those used as a chemically amplified resist. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium carbonates. By containing the basic compound [I] in the composition, the diffusion length of the acid generated from the [B] compound can be appropriately controlled by exposure and the pattern developing property can be improved.

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

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

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

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

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

Of these basic compounds, heterocyclic amines are preferable, and 4-dimethylaminopyridine and 1,5-diazabicyclo [4,3,0] -5-nonene are more preferable.

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

[[J] quinone diazide compound]

[J] quinone diazide compounds are compounds which generate carbonic acid by irradiation with radiation. As the [J] quinone diazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as &quot; mother nucleus &quot;) and 1,2-naphthoquinone diazidesulfonic acid halide can be used.

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

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

Examples of the tetrahydroxybenzophenone include 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'- Tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, and 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone. have.

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

Examples of the hexahydroxybenzophenone include 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone Phenone, and the like.

Examples of the (polyhydroxyphenyl) alkane include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris -Tris (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, - [1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] Ethylidene] bisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'- tetramethyl-1,1'-spirobindene- , 6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavone and the like.

Examples of other parent nuclei include 2- [2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7- 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-naphthoquinone diazidesulfonic acid halide, 1,2-naphthoquinonediazidesulfonic acid chloride is preferable. Examples of the 1,2-naphthoquinonediazidesulfonic acid chloride include 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-5-sulfonic acid chloride and the like . Of these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is preferable.

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

In the condensation reaction of the phenolic compound or the mother nucleus with the 1,2-naphthoquinonediazide sulfonic acid halide, the amount is preferably 30% by mole to 85% by mole relative to the number of OH groups in the phenolic compound or the alcoholic compound 1,2-naphthoquinone diazidesulfonic acid halide corresponding to 50 mol% to 70 mol% can be used. The condensation reaction can be carried out according to a known method.

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

&Lt; Preparation method of positive radiation-sensitive composition for ejection nozzle type coating method &gt;

The composition is prepared by dissolving or dispersing in the organic solvent [C] by mixing the [A] polymer, the [B] compound and, if necessary, a suitable component and other optional components. For example, the composition can be prepared by mixing each component in a predetermined ratio in an organic solvent [C].

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

The present invention suitably includes an interlayer insulating film for a display element formed from the composition. In the method of forming an interlayer insulating film for a display element of the present invention,

(1) a step of applying the composition to a substrate while relatively moving the ejection nozzle and the substrate to form a coating film,

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

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

(4) heating the developed coating film.

According to this forming method, the composition capable of forming a display element interlayer insulating film having high radiation sensitivity and excellent film thickness uniformity, which can be applied at a high speed, can be used for exposure, development and heating using radiation- It is possible to form an interlayer insulating film for a display element having a fine and precise pattern easily. In addition, the display element interlayer insulating film formed in this manner has no coating unevenness and has a high degree of flatness and can be suitably used for a display element such as a liquid crystal display element or an organic EL display element.

[Step (1)]

In this step, the composition is applied on a substrate by a discharge nozzle type coating method while relatively moving the discharge nozzle and the substrate to form a coating film. Preferably, the [C] organic solvent is removed by prebaking the application surface.

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

[Step (2)]

In this step, at least a part of the formed coating film is exposed to radiation. When exposure is performed, exposure is usually performed through a photomask having a predetermined pattern. As the radiation used for the exposure, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation including ultraviolet light of 365 nm is more preferable. The exposure dose is preferably 500 J / m &lt; 2 &gt; to 6,000 J / m &lt; 2 &gt;, and preferably 1,500 J / m &lt; / M &lt; 2 &gt; is more preferable.

[Step (3)]

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

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

[Step (4)]

In this step, the developed coating film is heated. For the heating, 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 [A] polymer to obtain a cured product. The heating temperature is, for example, about 120 ° C to 250 ° C. The heating time varies depending on the type of the heating apparatus, for example, about 5 minutes to 30 minutes for a hot plate and 30 minutes to 90 minutes for an oven. Further, a step baking method in which two or more heating steps are performed may be used. In this manner, a patterned thin film corresponding to the target interlayer insulating film for a display element can be formed on the surface of the substrate.

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

Example

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

<Synthesis of [A] Polymer>

[Synthesis Example 1]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of ADVN as a polymerization initiator and 200 parts by mass of diethylene glycol ethyl methyl ether as a solvent were added. Subsequently, 40 parts by mass of 1-ethoxyethyl methacrylate to give the structural unit (I), 40 parts by mass of glycidyl methacrylate to give an epoxy group-containing structural unit, 5 parts by mass of methacrylic acid 5 , 5 parts by mass of styrene, 10 parts by mass of 2-hydroxyethyl methacrylate, and 3 parts by mass of? -Methylstyrene dimer as a molecular weight regulator were charged and replaced with nitrogen, followed by gentle agitation. The temperature of the solution was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-1). The Mw of the polymer (A-1) was 9,000. The solid concentration of the polymer solution was 32.1 mass%.

[Synthesis Example 2]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of ADVN as a polymerization initiator and 200 parts by mass of diethylene glycol ethyl methyl ether as a solvent were added. Subsequently, 40 parts by mass of 2-tetrahydropyranyl methacrylate to give the structural unit (I), 40 parts by mass of glycidyl methacrylate to give an epoxy group-containing structural unit, methacrylic acid 5 parts by mass of styrene, 10 parts by mass of 2-hydroxyethyl methacrylate, and 3 parts by mass of? -Methylstyrene dimer as a molecular weight regulator were charged and replaced with nitrogen, followed by gentle agitation. The temperature of the solution was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-2). The Mw of the polymer (A-2) was 9,000. The solid concentration of the polymer solution was 31.3% by mass.

[Synthesis Example 3]

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (methyl 2-methylpropionate) as a polymerization initiator and 300 parts by mass of methyl isobutyl ketone as a solvent were placed. Subsequently, 40 parts by mass of 2-tetrahydropyranyl methacrylate to give the structural unit (I), 40 parts by mass of 3- (methacryloyloxymethyl) -3-ethyloxetane to give an epoxy group-containing structural unit, Then, 5 parts by mass of methacrylic acid and 15 parts by mass of 2-hydroxyethyl methacrylate, which give other structural units, were purged with nitrogen and stirred gently. The temperature of the solution was raised to 80 占 폚, and this temperature was maintained for 6 hours to obtain a polymer solution. The resulting polymer solution was then poured into excess heptane to reprecipitate the polymer. The supernatant heptane was removed by decantation. Thereafter, the resultant was filtered, and the resulting polymer was vacuum-dried for 24 hours to obtain a polymer (A-3). The Mw of the polymer (A-3) was 8,000.

[Synthesis Example 4]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of ADVN as a polymerization initiator and 200 parts by mass of diethylene glycol ethyl methyl ether as a solvent were added. Subsequently, 35 parts by mass of 1-n-butoxyethyl methacrylate to give the structural unit (I), 30 parts by mass of glycidyl methacrylate to give an epoxy group-containing structural unit, and a meta And 35 parts by mass of benzylic acid benzyl, and the mixture was purged with nitrogen, followed by gentle stirring. 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-4). The Mw of the polymer (A-4) was 10,000. The solid concentration of the polymer solution was 32.3 mass%.

[Synthesis Example 5]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (methyl 2-methylpropionate) as a polymerization initiator and 200 parts by mass of propylene glycol monomethyl ether acetate as a solvent were added. Subsequently, 67 parts by mass of 1-n-butoxyethyl methacrylate to give the structural unit (I), 10 parts by mass of methacrylic acid imparting other structural units and 23 parts by mass of benzyl methacrylate were charged, After that, it started stirring gently. The temperature of the solution was raised to 80 캜, and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (a-1). The Mw of the polymer (a-1) was 9,000. The solid concentration of the polymer solution was 30.3 mass%.

[Synthesis Example 6]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (methyl 2-methylpropionate) as a polymerization initiator and 200 parts by mass of propylene glycol monomethyl ether acetate as a solvent were added. Subsequently, 90 parts by mass of 1-benzyloxyethyl methacrylate to give the structural unit (I) and 6 parts by mass of 2-hydroxyethyl methacrylate and other 4 parts by mass of methacrylic acid, After the substitution, gentle stirring was started. 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 polymer (a-2) Mw was 9,000. The solid content concentration of the polymer solution was 31.2 mass%.

[Synthesis Example 7]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (methyl 2-methylpropionate) as a polymerization initiator and 200 parts by mass of propylene glycol monomethyl ether acetate as a solvent were added. Subsequently, 85 parts by mass of 2-tetrahydropyranyl methacrylate to give the structural unit (I), and 7 parts by mass of 2-hydroxyethyl methacrylate and 8 parts by mass of methacrylic acid After purging with nitrogen, stirring was started gently. The temperature of the solution was raised to 80 캜, and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (a-3). The Mw of the polymer (a-3) was 10,000. The solid concentration of the polymer solution was 29.2 mass%.

[Synthesis Example 8]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of ADVN as a polymerization initiator and 200 parts by mass of diethylene glycol ethyl methyl ether as a solvent were added. Subsequently, 52 parts by mass of glycidyl methacrylate for imparting an epoxy group-containing structural unit and 48 parts by mass of benzyl methacrylate for imparting other structural units were charged and after nitrogen substitution, gentle stirring was started. The temperature of the solution was raised to 80 캜, and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (a-4). The Mw of the polymer (a-4) was 10,000. The solid concentration of the polymer solution was 32.3 mass%.

[Synthesis Example 9]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of ADVN as a polymerization initiator and 200 parts by mass of diethylene glycol ethyl methyl ether as a solvent were added. Subsequently, 45 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate to give an epoxy group-containing structural unit and 45 parts by mass of benzyl methacrylate imparting other structural units and 10 parts by mass of methacrylic acid were added, After that, it started stirring gently. The temperature of the solution was raised to 80 DEG C and the temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (a-5). The Mw of the polymer (a-5) was 10,000. The solid content concentration of the polymer solution was 33.2 mass%.

&Lt; Preparation of positive radiation-sensitive composition for discharge nozzle type coating method &gt;

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

&Lt; [B] Compound &gt;

B-1 to B-5 are oxime sulfonate compounds. B-6 and B-7 are onium salts (B-6 is a tetrahydrothiophenium salt and B-7 is a sulfonium salt).

B-1: (5-Propylsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile (IRGACURE PAG 103 manufactured by Ciba Specialty Chemicals)

B-2: (5-Octylsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile (IRGACURE PAG 108 manufactured by Ciba Specialty Chemicals) represented by the above-

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

B-4: (Camphorsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile (CGI 1380 manufactured by Ciba Specialty Chemicals) represented by the above compound (iii)

B-5: (5-Octylsulfonyloxyimino) - (4-methoxyphenyl) acetonitrile (CGI 725 manufactured by Ciba Specialty Chemicals) represented by the above compound (v)

B-6: 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate

B-7: Benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate

<[C] Organic solvent>

(C1) an organic solvent (vapor pressure at 20 DEG C of 0.1 mmHg or more and less than 1 mmHg)

C-1-1: Diethylene glycol ethyl methyl ether (20 DEG C, 0.75 mmHg)

C-1-2: dipropylene glycol dimethyl ether (20 DEG C, 0.38 mmHg)

(C2) an organic solvent (vapor pressure at 20 DEG C of not less than 1 mmHg and not more than 20 mmHg)

C-2-1: Diethylene glycol dimethyl ether (20 DEG C, 1.3 mmHg)

C-2-2: Propylene glycol monomethyl ether acetate (20 DEG C, 3.75 mmHg)

C-2-3: Cyclohexanone (20 DEG C, 3.4 mmHg)

The solvent used in the comparative example

1,4-dioxane (20 DEG C, 29 mmHg)

Ethylene glycol (20 DEG C, 0.08 mmHg)

&Lt; [D] Surfactant &gt;

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

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

<[E] polyfunctional (meth) acrylate compound>

E-1: Ethylene glycol dimethacrylate

E-2: Trimethylolpropane trimethacrylate

E-3: Pentaerythritol tetraacrylate

<[F] Antioxidant>

F-1: 2,6-di-t-butyl-4-cresol

F-2: 4-methoxyphenol

<[G] Epoxy Compound>

G-1: Bisphenol A diglycidyl ether (a polycondensate of 4,4'-isopropylidenediphenol and 1-chloro-2,3-epoxypropane)

G-2: 3,4-Epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate

<[H] Adhesion preparation>

H-1:? -Glycidoxypropyltrimethoxysilane

H-2:? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane

H-3:? -Methacryloxypropyltrimethoxysilane

&Lt; [I] Basic compound &gt;

I-1: 4-Dimethylaminopyridine

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

[Example 1]

3 parts by mass of (B-1) as the [B] compound, (C1) as the organic solvent (B-1) were added to a solution containing 100 parts by mass (solid content) of the polymer (A- (D-1) as a surfactant were mixed and filtered with a membrane filter having a pore size of 0.2 占 퐉 to obtain a positive electrode for a discharge nozzle type coating method A radiation-sensitive composition was prepared.

[Examples 2 to 16 and Comparative Examples 1 to 4]

Each composition was prepared in the same manner as in Example 1 except that kinds and blending amounts of the respective components were changed as shown in Table 1. Further, the numerical values of the [C] organic solvent in Table 1 are the mass% ratios of (C1) the organic solvent and (C2) the organic solvent. In Table 1, &quot; - &quot; means that the corresponding component was not used.

<Evaluation>

Using the respective compositions thus prepared, the following evaluations were carried out. The results are shown in Table 1.

[Viscosity (mPa · s)]

Viscosity (mPa 占 퐏) of the composition at 25 占 폚 was measured using an E-type viscometer (VISCONIC ELD.R, manufactured by Toki Sangyo Co., Ltd.).

[Solid content concentration (% by mass)]

0.3 g of each composition was precisely weighed on an aluminum plate and about 1 g of diethylene glycol dimethyl ether was added and dried on a hot plate at 175 DEG C for 60 minutes to give a solid content concentration %).

[Appearance of Coating Film]

Each composition thus prepared was coated on a chromium-deposited glass of 550 x 650 mm by using a slit die coater (TR632105-CL manufactured by Tokyo Ohka Kogyo Co., Ltd.), dried under reduced pressure to 0.5 Torr, and prebaked on a hot plate at 100 캜 for 2 minutes, And exposed at an exposure amount of 2,000 J / m &lt; 2 &gt; to form a film having a film thickness of 4 mu m from the upper surface of the chromium film-forming glass. Under the sodium lamp, the appearance of the coating film was visually observed. At this time, the stripe unevenness (the coating direction or one or a plurality of straight line streaks formed in the direction crossing the streak) in the entire coating film, fog spots (cloud spots), pin mark spots And the appearance of the dot-shaped dirt). "A" (judged to be good), "B" (slightly judged to be defective), and "C" (judged to be defective) to be clearly visible were judged as "A" .

[Film thickness uniformity (%)]

The film thickness of the coating film on the chromium film-formed glass produced as described above was measured using a film thickness measuring apparatus (manufactured by Dainippon Screen, Lambda ACE). The film thickness uniformity was calculated by measuring the film thickness at nine measurement points and by the following formula. (X [mm], Y [mm]) satisfy the following equations: (275,20), (275,30), (275,60) 275, 100), (275, 325), (275, 550), (275, 590), (275, 620), (275, 630). The case where the film thickness uniformity was more than 1.80% and the case where the film thickness uniformity was not more than 2% was evaluated as good, and the case where the film thickness uniformity was not more than 1.80% was judged as good.

Film thickness uniformity (%) = {FT (X, Y) max-FT (X, Y) min}

FT (X, Y) max is the maximum value among the film thicknesses at nine measurement points, FT (X, Y) min is the minimum value among the film thicknesses at nine measurement points, FT avg. is the average value of the film thickness at nine measurement points.

[High-speed coating property (mm / sec.)]

The coating liquid was applied on a 550 mm x 650 mm non-alkali glass substrate using a slit die coater, and the coating liquid was applied from the nozzle to a coating liquid such that the distance between the base and the nozzle was 150 mu m, And the moving speed of the nozzle was varied in the range of 120 mm / sec. To 220 mm / sec. To determine the maximum speed at which striped irregularity due to liquid breakage did not occur. At this time, 180 mm / sec. It was judged that the high-speed coating property was good when no stripe-shaped unevenness occurred.

[Radiation sensitivity (J / m 2)]

Hexamethyldisilazane (HMDS) was applied on a chromium-deposited glass of 550 x 650 mm and heated at 60 占 폚 for 1 minute. Each composition was coated on the chromium film-coated glass after the treatment with hexamethyldisilazane using a slit die coater (TR632105-CL, manufactured by Tokyo Ohka Kogyo Co., Ltd.), the solvent was removed under vacuum by setting the ultimate pressure to 100 Pa, And further baked at 90 DEG C for 2 minutes to form a coating film having a film thickness of 3.0 mu m. Subsequently, the coating film was irradiated with radiation with varying exposure dose through a mask having a pattern of 60 占 퐉 line-and-space (10: 1) using an exposure machine (manufactured by Canon Inc., MPA-600FA) Was developed by a puddle method at 25 DEG C with an aqueous solution of tetramethylammonium hydroxide having the concentration shown in Table 1. [ 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. When the value is 500 J / m &lt; 2 &gt; or less, it is determined that the sensitivity is good.

[Transmittance (%)]

Using the spinner, each composition thus prepared was coated on a glass substrate and prebaked on a hot plate at 90 DEG C for 2 minutes to form a coating film having a film thickness of 3.0 mu m. The coated film was exposed at an exposure dose of 700 J / m &lt; 2 &gt; and then heated in a clean oven at 220 DEG C for 1 hour to obtain a cured film. Then, the transmittance at a wavelength of 400 nm was measured using a spectrophotometer (150-20 type double beam manufactured by Hitachi, Ltd.). The transmittance was found to be good when the measured value (%) was close to 100% and the transparency was judged to be bad when the measured value (%) was less than 90%.

[Heat resistance transparency (%)]

The substrate measured in the evaluation of the transmittance was further heated in a clean oven at 250 DEG C for 1 hour to measure the light transmittance before and after heating in the same manner as in the evaluation of the transmittance, Respectively. The closer the value was to 0%, the better the heat-resistant transparency. If the value exceeded 5%, the heat-resistant transparency was judged to be poor.

Heat resistance transparency (%) = Transmittance before heating (%) - Transmittance after heating (%)

From the results shown in Table 1, it can be seen that Examples 1 to 16 using this composition can form a coating film having high radiation sensitivity and excellent film thickness uniformity as compared with the compositions of Comparative Examples 1 to 4, And the appearance of the coating film was also good.

In Examples 3 to 16 in which (C) an organic solvent and (C2) an organic solvent were combined as the organic solvent, (C1) the film thickness uniformity It became clear that it was better than this. In Examples 3 to 11, in which the content of the organic solvent (C2) is 50 mass% or less based on the total amount of the organic solvent (C1) and the organic solvent (C2), the content of the organic solvent (C2) It is clear that the appearance and the film thickness uniformity of the coating film are particularly excellent as compared with Example 12, which is 70% by mass based on the total amount of the solvent and the organic solvent (C2).

On the other hand, Examples 13 to 16 containing the [E] polyfunctional (meth) acrylate compound, [F] antioxidant and [G] epoxy compound, which are suitable components of the composition, It was found that the transmittance and the heat resistance transparency were better than those of Comparative Examples 1 to 12.

INDUSTRIAL APPLICABILITY The positive radiation-sensitive composition for a discharge nozzle coating method of the present invention can form an interlayer insulating film for a display element having a high degree of radiation sensitivity and a high degree of flatness (uniformity in film thickness) without coating unevenness, Application is possible. Therefore, the composition is suitable as a material for forming an interlayer insulating film for a display element such as a liquid crystal display element or an organic EL display element.

Claims (11)

[A] a polymer having a structural unit (I) containing a group represented by the following formula (1) and an epoxy group-containing structural unit in the same or different polymer molecules,
[B] at least one compound selected from the group consisting of an oxime sulfonate compound and an onium salt compound, and
[C] Organic solvent
, The solid content concentration is 10 mass% or more and 30 mass% or less, the viscosity at 25 占 폚 is 2.0 mPa 占 퐏 or more and 12 mPa 占 퐏 or less,
(C) an organic solvent having a vapor pressure at 20 DEG C of not less than 0.1 mmHg and not more than 1 mmHg, (C2) an organic solvent having a vapor pressure at 20 DEG C of not less than 1 mmHg and not more than 20 mmHg,
(C2) the content of the organic solvent is 10% by mass or more and 50% by mass or less based on the total amount of the organic solvent (C1) and the organic solvent (C2)
(C2) the organic solvent is selected from the group consisting of diethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, cyclohexanone, n-butyl acetate, methyl isobutyl ketone, 3- Wherein the solvent is at least one organic solvent selected from the group consisting of methyl methoxypropionate and methyl methoxypropionate.

(Wherein R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, with the proviso that some or all of the hydrogen atoms of the alkyl group, cycloalkyl group and aryl group may be substituted R ³ is an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group or a group represented by -M (R ^3m ) ₃ , provided that R ¹ and R ² are not hydrogen atoms; R ^{3 m} is an alkyl group with the proviso that R ¹ and R ³ are connected to form a cyclic structure together with the carbon atom to which they are bonded, Ether may be formed). delete delete The method according to claim 1,
[D] at least one surfactant selected from the group consisting of a fluorine-based surfactant and a silicone-based surfactant,
Wherein the content of the [D] surfactant is 0.01 parts by mass or more and 2 parts by mass or less based on 100 parts by mass of the polymer [A]. The method according to claim 1,
A positive radiation-sensitive composition for a dispensing nozzle-type coating method further comprising a [E] polyfunctional (meth) acrylate compound. The method according to claim 1,
[F] A positive radiation-sensitive composition for a dispensing nozzle-type coating method further comprising an antioxidant. The method according to claim 1,
[G] A positive radiation-sensitive composition for a discharge nozzle coating method, which further contains a compound having two or more epoxy groups in one molecule. The method according to claim 1,
(C1) the organic solvent is at least one organic solvent selected from the group consisting of diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, benzyl alcohol and dipropylene glycol monomethyl ether, A positive radiation-sensitive composition for a nozzle-type coating method. delete An interlayer insulating film for a display element formed of a positive radiation-sensitive composition for a discharge nozzle coating method according to any one of claims 1 to 8. (1) A positive radiation-sensitive composition for a discharge nozzle coating method according to any one of claims 1 to 8, which is applied on a substrate while relatively moving the discharge nozzle and the substrate to form a coating film Forming process,
(2) a step of irradiating at least a part of the formed coating film with radiation,
(3) a step of developing the coating film irradiated with the radiation, and
(4) a step of heating the developed coating film
Of the interlayer insulating film for a display element.