TWI572627B - Radiation-sensitive composition, interlayer insulating film for display device and method for fabricating the same - Google Patents

Description

Radiation-sensitive linear composition, interlayer insulating film for display element, and method of forming the same

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

In the display element, an interlayer insulating film for a display element is usually provided for the purpose of insulating wirings arranged in a layer shape. As a material for forming the interlayer insulating film for a display element, since the number of steps for obtaining a desired pattern shape is small, and the obtained interlayer insulating film for a display element is required to have high flatness, a radiation sensitive resin composition is widely used. In addition to the flatness required for the interlayer insulating film for display elements, excellent surface hardness, solvent resistance, heat resistance, voltage holding ratio, and the like are required for such a radiation-sensitive resin composition.

A composition containing a crosslinking agent, an acid generator, and an alkali-soluble resin is known as such a radiation-sensitive resin composition (refer to Japanese Patent Laid-Open No. 2004-4669) Bulletin). The above-mentioned alkali-soluble resin refers to a resin having a protective group (a group which is insoluble or poorly soluble in an aqueous alkali solution and which is dissociable by the action of an acid), and which becomes soluble or soluble in an aqueous alkali solution after dissociation of the protective group. . Further, other radiation-sensitive resin compositions have a resin containing an acetal structure or a ketal structure and an epoxy group, and a radiation-sensitive resin composition containing an acid generator (refer to Japanese Laid-Open Patent Publication No. 2004-264623).

However, in the conventional radiation sensitive resin composition described above, since the radiation sensitivity is insufficient, there is a problem that a fine and delicate pattern cannot be easily formed.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-4669

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-264623

The present invention has been made in view of the above-described circumstances, and an object thereof is to provide a radiation-sensitive linearity of an interlayer insulating film for a display element which has higher sensitivity and can be formed to have excellent surface hardness, solvent resistance, heat resistance, and voltage holding ratio. The composition is an interlayer insulating film for a display element formed using the radiation-sensitive composition and a method for forming the same.

The invention formed to solve the above problems is a radiation sensitive linear composition comprising: [A] a polymer having a structural unit (I) having an acid-dissociable group, a structural unit (II) containing a polymerizable group, and a structural unit (III) represented by the following formula (1) (hereinafter also referred to as " [A] Polymer"); and [B] Radiation-sensitive acid generator.

In the formula (1), R ¹ is a hydrogen atom or a methyl group; and R ² is an alkyl group, an alkenyl group, an alkynyl group or a decyloxyalkyl group having a carbon number of 6 to 30 or a crosslinked cyclic hydrocarbon group having a carbon number of 4 to 30. Wherein a part of the hydrogen atom possessed by the above alkyl group, alkenyl group, alkynyl group, decyloxyalkyl group and crosslinked cyclic hydrocarbon group may be substituted with a hydroxyl group or a carboxyl group.

In the radiation-sensitive linear composition, since the [A] polymer has a structural unit (III) containing a group represented by R ² , the flexibility before curing is improved, and as a result, the diffusion of acid generated during exposure is promoted. Further improve the sensitivity. In the radiation-sensitive composition, the [A] polymer has a polymerizable group-containing structural unit (II), and can form a display element having sufficient surface hardness, solvent resistance, heat resistance, and voltage holding ratio. The film is cured with an interlayer insulating film or the like.

It is preferable that the radiation sensitive composition further contains one or more [C]. A compound having a (meth)acrylonium group and a molecular weight of 1,000 or less (hereinafter also referred to as "[C] compound"). By further containing the [C] compound, the radiation-sensitive composition can form a cured film which further improves surface hardness, solvent resistance, heat resistance, and voltage holding ratio.

The acid dissociable group in the above structural unit (I) is preferably represented by the following formula (2).

In the formula (2), R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group or an aryl group; wherein a part of a hydrogen atom of the alkyl group, the alicyclic hydrocarbon group or the aryl group or All may be substituted; in addition, there is no case where both R ³ and R ⁴ are a hydrogen atom; and R ⁵ is an alkyl group, an alicyclic hydrocarbon group, an aralkyl group, an aryl group or a group represented by -M(R ⁶ ) ₃ group; M is Si, Ge or of Sn; R ⁶ is alkyl; wherein the alkyl part, an alicyclic hydrocarbon group, aryl group and aralkyl group of R ⁵ and R ⁶ are hydrogen atoms or having all which may be substituted; R ³ and R ⁵ may be bonded to each other to form a cyclic structure together with an ether oxygen atom and R ⁵ carbon atoms are bonded to R ³ are bonded.

The acid dissociable group represented by the above formula (2) has a structure which is easily dissociated by the action of an acid generated by the [B] sensitizing radioactive acid generator. Therefore, the sense of radiation The composition can further improve the sensitivity by including such an [A] polymer containing an acid-dissociable group, and can easily form a fine and delicate pattern.

The polymerizable group in the above structural unit (II) is preferably an epoxy group. Since the [A] polymer contains an epoxy group as a polymerizable group, the cured film such as an interlayer insulating film for a display element formed of the radiation sensitive composition can further improve surface hardness, solvent resistance, heat resistance, and voltage holding ratio. . Here, the epoxy group is a concept including an oxiranyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure).

The content of the structural unit (III) in the [A] polymer is preferably 3% by mass or more and 50% by mass or less. As described above, by setting the content ratio of the structural unit (III) in the [A] polymer to the above range, it is possible to further promote the diffusion of the acid and further improve the sensitivity.

The [C] compound is preferably a compound having a skeleton derived from a diol structure of 2 to 12 carbon atoms, a skeleton derived from trimethylolpropane, a skeleton derived from pentaerythritol, or a skeleton derived from dipentaerythritol. As described above, by including the above specific compound as the [C] compound, the surface hardness, solvent resistance, heat resistance, and voltage holding ratio of the cured film of the interlayer insulating film for a display element to be formed can be further improved.

The content of the [C] compound is preferably 1% by mass or more and 50% by mass or less in terms of solid content. In the radiation-sensitive composition, the content of the [C] compound is in the above range, and the surface hardness, solvent resistance, heat resistance, and voltage holding ratio of the cured film such as the interlayer insulating film for a display element to be formed can be made. Excellent.

The radiation sensitive composition is suitable as a material for forming an interlayer insulating film for a display element. In addition, the present invention also suitably comprises forming the radiation-sensitive composition An interlayer insulating film is used for the display element.

The method for forming an interlayer insulating film for a display device of the present invention comprises: (1) a step of forming a coating film on a substrate using the radiation sensitive composition; and (2) a step of irradiating at least a portion of the coating film with radiation; 3) a step of developing the above-mentioned coating film irradiated with radiation; and (4) a step of heating the above-mentioned coating film which has been developed.

According to this formation method, it is possible to form an interlayer insulating film for a display element which is excellent in surface hardness, solvent resistance, heat resistance, and voltage holding ratio. In addition, by using the radiation-sensitive composition having excellent sensitivity, it is possible to easily form an interlayer insulating film for a display element having a fine and delicate pattern. Therefore, the formed interlayer insulating film for a display element can be suitably used for a display element such as a liquid crystal display element or an organic electroluminescence (EL) display element.

In addition, the term "radiation" of the "radiation-sensitive composition" in the present specification means a concept including visible light rays, ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like.

As described above, the radiation sensitive composition of the present invention can easily form an interlayer insulating film for a display element having a fine and delicate pattern because of its excellent sensitivity. In addition, the radiation sensitive composition can form an interlayer insulating film for a display element which is excellent in surface hardness, solvent resistance, heat resistance, and voltage holding ratio. Therefore, the radiation-sensitive composition is suitably used 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.

<Sense Radiation Composition>

The radiation sensitive composition of the present invention contains [A] a polymer and a [B] radiation sensitive acid generator as essential components, and contains a [C] compound as a suitable component. Further, the radiation sensitive composition may contain other optional components within a range that does not impair the effects of the present invention. Hereinafter, each component will be described in detail.

<[A] Polymer>

[A] The polymer is a polymer having a structural unit (I) having an acid-dissociable group, a structural unit (II) containing a polymerizable group, and a structural unit (III) represented by the above formula (1). Further, the [A] polymer may contain other structural units within the range not impairing the effects of the present invention. Further, the [A] polymer may have two or more types of structural units. Hereinafter, each structural unit will be described in detail.

[Structural unit (I)]

The structural unit (I) is a structural unit containing an acid dissociable group. The acid dissociable group is dissociated by the action of an acid generated from the [B] sensitizing radioactive acid generator upon exposure, and a polar group is generated, so that the [A] polymer which is insoluble or poorly soluble in the aqueous alkali solution becomes a pair. The aqueous alkali solution is soluble. The radiation sensitive composition can have good sensitivity because the [A] polymer has such a structural unit (I).

The structural unit (I) is not particularly limited as long as it is a structural unit containing an acid-dissociable group, and is preferably an acid-dissociable group-containing structure represented by the above formula (2) from the viewpoint of easy dissociation by an acid. unit. In the above formula (2), R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group or an aryl group. Here, some or all of the hydrogen atoms of the alkyl group, the alicyclic hydrocarbon group or the aryl group may be substituted. Further, there is no case where both R ³ and R ⁴ are hydrogen atoms. R ⁵ is an alkyl group, an alicyclic hydrocarbon group, an aralkyl group, an aryl group or a group represented by -M(R ⁶ ) ₃ . M is Si, Ge or Sn. R ⁶ is an alkyl group. Wherein a portion of the R ⁵ alkyl group, an alicyclic hydrocarbon group, aryl group and arylalkyl group and R ⁶ being an alkyl group having all of hydrogen atoms or may be substituted. R ³ and R ⁵ may be bonded to form a cyclic ether structure.

Examples of the alicyclic hydrocarbon group represented by the above R ³ and R ⁴ include an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Further, the alicyclic hydrocarbon group having 3 to 20 carbon atoms may be a polycyclic ring. Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a borneol group, a norbornyl group, and an adamantyl group.

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

Examples of the substituent of the substitutable alkyl group, the alicyclic hydrocarbon group and the aryl group represented by the above R ³ and R ⁴ include a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, and an alicyclic hydrocarbon group ( For example, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, borneol, norbornyl, adamantyl, etc.), aryl (eg phenyl, naphthyl, etc.), alkoxy (eg eg 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 or an octyloxy group; and an acyl group (for example, an acetyl group) a carbonyl group having 2 to 20 carbon atoms such as a propionyl group, a butyryl group or an isobutyryl group, or an acyloxy group (for example, an acetoxy group, a butyryloxy group, a third butyryloxy group or a third valeryloxy group). a 2 to 10 acyloxy group or the like, an alkoxycarbonyl group (for example, an alkoxycarbonyl group having 2 to 20 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group or a propoxycarbonyl group) or a halogenated alkyl group (for example, a methyl group) , ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-dodecyl, n-tetradecyl, n-octadecyl, etc., linear alkyl, isopropyl , isobutyl, tert-butyl, An alkyl group such as a branched alkyl group such as a pentyl group, a 2-hexyl group or a 3-hexyl group; or a part or all of a hydrogen atom of an alicyclic hydrocarbon group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a norbornyl group or an adamantyl group; a group substituted with a halogen atom, etc.), a hydroxyalkyl group (for example, a hydroxymethyl group, etc.), or the like.

The alkyl group, the alicyclic hydrocarbon group and the aryl group represented by the above R ⁵ can be explained by the respective groups represented by the above R ³ and R ⁴ . Further, the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group or a n-propyl group. The aralkyl group represented by the above R ⁵ may, for example, be a benzyl group, a phenethyl group, a naphthylmethyl group or a naphthylethyl group.

In the group represented by -M(R ⁶ ) 3 of the above R ⁵ , the alkyl group represented by R ⁶ may be described by using the alkyl group represented by R ³ and R ⁴ described above.

The cyclic ether structure in which R ³ and R ⁵ are bonded to each other is preferably a cyclic ether structure having a ring number of 3 to 20, more preferably a cyclic ether structure having a ring number of 5 to 8, more preferably tetrahydrofuran. And tetrahydropyran.

The group represented by the above formula (2) is, for example, a group represented by the following formula Mission and so on.

Examples of the monomer which provides the above structural unit (I) include 1-ethoxyethyl methacrylate, 1-methoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, and methyl group. 1-Isobutoxyethyl acrylate, 1-t-butoxyethyl methacrylate, 1-(2-chloroethoxy)ethyl methacrylate, 1-(2-ethylhexyl methacrylate) Ethyl)ethyl ester, 1-n-propoxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, 1-(2-cyclohexylethoxy)ethyl methacrylate, methacrylic acid 1-benzyloxyethyl ester, 2-tetrahydropyranyl methacrylate, 1-ethoxyethyl acrylate, 1-methoxyethyl acrylate, 1-n-butoxyethyl acrylate, acrylic acid 1 -isobutoxy B Ester, 1-t-butoxyethyl acrylate, 1-(2-chloroethoxy)ethyl acrylate, 1-(2-ethylhexyloxy)ethyl acrylate, 1-n-propyloxyethyl acrylate Ester, 1-cyclohexyloxyethyl acrylate, 1-(2-cyclohexylethoxy)ethyl acrylate, 1-benzyloxyethyl acrylate, 2-tetrahydropyranyl acrylate, 5,6- Bis(1-(trimethyldecyloxy)ethoxy)carbonyl)-2-norbornene, 5,6-bis(1-(trimethylformamoxy)ethoxy)carbonyl)- 2-norbornene, 5,6-bis(1-methoxyethoxycarbonyl)-2-norbornene, 5,6-bis(1-(cyclohexyloxy)ethoxycarbonyl)-2 -norbornene, 5,6-bis(1-(benzyloxy)ethoxycarbonyl)-2-norbornene, p--1-ethoxyethoxystyrene or m-ethoxylate Ethoxystyrene, p--1-methoxyethoxystyrene or m-methoxyethoxystyrene, p--1-n-butoxyethoxystyrene or m--1- n-Butoxyethoxystyrene, p--1-isobutoxyethoxystyrene or m-Isobutoxyethoxystyrene, p--1-(1,1-dimethyl Ethoxy)ethoxy styrene or m-(1,1-dimethylethoxy)ethoxystyrene, p--1-(2- Ethoxy)ethoxy styrene or m-(2-chloroethoxy)ethoxystyrene, p--1-(2-ethylhexyloxy)ethoxystyrene or m-1 -(2-ethylhexyloxy)ethoxystyrene, p--1-n-propoxyethoxystyrene or m--1-n-propoxyethoxystyrene, p-hexacyclohexyl Oxyethoxy styrene or m-hexacyclohexyloxyethoxystyrene, p--1-(2-cyclohexylethoxy)ethoxystyrene or m-(2-cyclohexyl) Ethoxy)ethoxystyrene, p--1-benzyloxyethoxystyrene or m-benzyloxyethoxystyrene.

The monomer which provides the structural unit (I) in these monomers is preferably a structural unit containing an acid-dissociable group represented by the above formula (2), more preferably 1-ethoxyethyl methacrylate or methacrylic acid 1 - n-butoxyethyl ester, 2-tetrahydropyran methacrylate The base ester, 1-benzyloxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, and particularly preferably 2-tetrahydropyranyl methacrylate.

The content of the structural unit (I) in the polymer is not particularly limited as long as the effect of the present invention is exerted, but the structural unit (I) is the same as all the structural units contained in the [A] polymer. The content of the monomer is preferably 5% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 70% by mass or less, and particularly preferably 15% by mass or more and 65% by mass or less.

[Structural unit (II)]

The structural unit (II) is a structural unit containing a polymerizable group. By the structural unit (II) of the [A] polymer, the interlayer insulating film for a display element formed of the radiation-sensitive composition can have more excellent surface hardness, heat resistance, solvent resistance, and voltage holding ratio.

The structural unit (II) is not particularly limited as long as it is a structural unit containing a polymerizable group, and examples thereof include an epoxy group-containing structural unit (II-1) and a (meth)acrylonyl group-containing structural unit (II-2). ) as a preferred structural unit. Hereinafter, the epoxy group-containing structural unit and the (meth)acryl fluorenyl group-containing structural unit will be described in detail.

[Alkoxy group-containing structural unit (II-1)]

The epoxy group-containing structural unit (II-1) is not particularly limited as long as it has a structural unit having an epoxy group in its structural unit. Examples of the epoxy group-containing monomer which provides such a structural unit (II-1) include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3-methyl acrylate. -3,4-epoxybutyl acrylate, 3-ethyl-3,4-epoxybutyl methacrylate, (A 5,6-epoxyhexyl acrylate, 5-methyl-5,6-epoxyhexyl methacrylate, 5-ethyl-5,6-epoxyhexyl methacrylate, (methyl) 6,7-epoxyheptyl acrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexyl (meth)acrylate Ethyl ester, 3,4-epoxycyclohexyl propyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl hexyl (meth)acrylate, acrylic acid 3, 4-epoxycyclohexylmethyl ester, 3,4-epoxycyclohexylethyl acrylate, 3,4-epoxycyclohexyl propyl acrylate, 3,4-epoxycyclohexyl acrylate, 3,4-acrylic acid Ethylene oxide group-containing (meth)acrylic compound such as epoxycyclohexylhexyl ester; o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α a vinylbenzyl glycidyl ether such as methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether or α-methyl-p-vinylbenzyl glycidyl ether; O-vinylphenyl glycidyl ether, m-vinylphenyl glycidyl ether Vinyl phenyl glycidyl ethers such as p-vinylphenyl glycidyl ether; 3-propenyloxymethyloxetane, 3-propenyloxymethyl-3-methyloxetane , 3-propenyloxymethyl-3-ethyloxetane, 3-propenyloxymethyl-3-phenyloxetane, 3-(2-propenyloxyethyl) Oxetane, 3-(2-propenyloxyethyl)-3-ethyloxetane, 3-(2-propenyloxyethyl)-3-ethyloxocyclo Butane, 3-(2-propenyloxyethyl)-3-phenyloxetane, 3-methylpropenyloxymethyloxetane, 3-methylpropenyloxy Methyl-3-methyloxetane, 3-methacryloxymethyl-3-ethyloxetane, 3-methylpropenyloxymethyl-3-phenyloxy Heterocyclic butane, 3-(2-methylpropenyloxy) Oxycyclobutane, 3-(2-methylpropenyloxyethyl)-3-ethyloxetane, 3-(2-methylpropenyloxyethyl)-3- Ethyloxetane, 3-(2-methylpropenyloxyethyl)-3-phenyloxetane, 2-propenyloxymethyloxetane, 2-propene醯oxymethyl-2-methyloxetane, 2-propenyloxymethyl-2-ethyloxetane, 2-propenyloxymethyl-2-phenyloxalate Cyclobutane, 2-(2-propenyloxyethyl)oxetane, 2-(2-propenyloxyethyl)-2-ethyloxetane, 2-(2- Propylene methoxyethyl)-2-ethyloxetane, 2-(2-propenyloxyethyl)-2-phenyloxetane, 2-methylpropenyloxymethyl Oxycyclobutane, 2-methacryloxymethyl-2-methyloxetane, 2-methylpropenyloxymethyl-2-ethyloxetane, 2 -Methacryloxymethyl-2-phenyloxetane, 2-(2-methylpropenyloxyethyl)oxetane, 2-(2-methylpropeneoxime Benzyl)-2-ethyloxetane, 2-(2-methylpropenyloxyethyl)-2-ethyloxetane, 2-(2-methylpropane An oxetanyl group-containing (meth)acrylic compound such as an enemethoxyethyl)-2-phenyloxetane.

Among the above epoxy group-containing monomers, from the viewpoint of copolymerization reactivity with other monomers and developability of the radiation-sensitive composition, glycidyl methacrylate and 2-methyl methacrylate are preferable. Glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-methylpropenyloxymethyl-3-methyloxane Butane, 3-methacryloxymethyl-3-ethyloxetane. Further, these monomers may be used alone or in combination of two or more.

[Structural unit containing (meth)acrylinyl group (II-2)]

The structural unit (II-2) containing a (meth) acrylonitrile group has as a poly The structural unit of the (meth) propylene fluorenyl group of a synth group is not specifically limited.

The method of introducing the structural unit (II-2) into the [A] polymer is, for example, a polymer of an unsaturated isocyanate compound and a monomer containing an unsaturated compound having at least one hydroxyl group in one molecule (hereinafter also referred to as A method of carrying out a reaction such as "[A1] polymer").

The monomer used for the synthesis of the [A1] polymer may, for example, be a hydroxyalkyl (meth)acrylate, a dihydroxyalkyl (meth)acrylate or a (6-hydroxyhexyloxy)alkyl (meth)acrylate. Base ester and the like.

Examples of the hydroxyalkyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Examples of the dihydroxyalkyl (meth)acrylate include 2,3-dihydroxypropyl (meth)acrylate, 1,3-dihydroxypropyl (meth)acrylate, and (meth)acrylic acid 3. 4-dihydroxybutyl ester and the like. The (6-hydroxyhexyloxy)alkyl (meth)acrylate may, for example, be 2-(6-hydroxyhexyloxy)ethyl (meth)acrylate or 3-(6) (meth)acrylic acid. -Hydroxyhexyloxy)propyl ester and the like.

Among these monomers, from the viewpoints of copolymerization reactivity and reactivity with an isocyanate compound, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and methacrylic acid 2 are preferable. - hydroxyethyl ester, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate. Further, these monomers may be used alone or in combination of two or more.

The [A1] polymer obtained in the above manner can be in a state of a polymerization solution For the synthesis of the [A] polymer, the [A1] polymer may also be temporarily separated from the solution for the synthesis of the [A] polymer.

Examples of the unsaturated isocyanate compound include an isocyanate group-containing derivative of (meth)acrylic acid. Examples of the unsaturated isocyanate compound include 2-(methyl)propenyloxyethyl isocyanate, 4-(methyl)propenyloxybutyl isocyanate, and 2-(2-(meth)acrylate). Isocyanate ethoxy)ethyl ester, 1,1-(bis(meth)acryloxymethyl)ethyl isocyanate, and the like. Further, the unsaturated isocyanate compounds may be used singly or in combination of two or more.

The commercial product of the unsaturated isocyanate compound is, for example, a commercially available product of 2-acetyl methoxyethyl isocyanate, Karenz AOI (manufactured by Showa Denko KK), and 2-methyl propylene methoxy ethoxylate isocyanate. Commercial product Karenz MOI-EG (manufactured by Showa Denko) and 1,1-(dipropylene hydride) are commercially available as Karenz MOI (manufactured by Showa Denko) and 2-(2-isocyanate ethoxy)ethyl methacrylate. Commercial product of oxymethyl)ethyl ester, Karenz BEI (manufactured by Showa Denko), and the like.

Among these unsaturated isocyanate compounds, from the viewpoint of reactivity with the [A1] polymer, 2-acryloxyethyl isocyanate, 2-methylpropenyloxyethyl isocyanate, and 4-methylpropenyloxybutyl isocyanate or 2-(2-isocyanate ethoxy)ethyl methacrylate, 1,1-(bispropenyloxymethyl)ethyl isocyanate.

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

The catalyst may, for example, be di-n-butyltin (IV) dilaurate or the like. Examples of the polymerization inhibitor include p-methoxyphenol and the like.

Other methods for introducing the structural unit (II-1) into the [A] polymer include, for example, a compound having a vinyl ether group and a (meth) propylene fluorenyloxy group and having at least one carboxyl group in one molecule. A method of reacting a polymer of a monomer of an unsaturated compound (hereinafter also referred to as "[A2] polymer").

The method of synthesizing the [A2] polymer is, for example, a method of polymerizing a carboxyl group-containing monomer, and the like, from the viewpoint of obtaining the material and facilitating the synthesis.

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

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

[Chemical 4] H ₂ C=CR ⁷ -COO-R ⁸ -O-CH=CHR ⁹ (3)

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

Examples of the divalent linking group represented by the above R ⁸ include a linear, branched or cyclic alkylene having 2 to 18 carbon atoms, an alkoxyalkylene group having 2 to 20 carbon atoms, and carbon. The number of 2 to 8 halogenated alkyl groups, the terminal hydroxyl group-containing polyethylene glycol skeleton, the terminal hydroxyl group-containing polypropylene glycol skeleton, the terminal hydroxyl group-containing polybutylene glycol skeleton, the aryl group, and the like. The monovalent organic group represented by the above R ⁹ may, for example, be a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or a substituted aromatic group having 6 to 11 carbon atoms.

Examples of the compound having a vinyl ether group and a (meth) acryloxy group represented by the above formula (3) include 2-vinyloxyethyl (meth)acrylate and 3-vinyloxy (meth)acrylate. Propyl propyl ester, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, (A) 1-methyl-3-vinyloxypropyl acrylate, 1-vinyloxymethylpropyl (meth)acrylate, 2-methyl-3-vinyloxypropyl (meth)acrylate, 1,1-dimethyl-2-vinyloxyethyl (meth)acrylate, 3-vinyloxybutyl (meth)acrylate, 1-methyl-2-vinyloxypropyl (meth)acrylate , 2-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxy (meth)acrylate Methylcyclohexylmethyl ester, 3-vinyloxymethylcyclohexylmethyl (meth)acrylate, 2-vinyloxymethylcyclohexylmethyl (meth)acrylate, (meth)acrylic acid to ethylene oxide Methyl phenyl methyl ester, m-vinyloxymethyl phenyl methyl (meth) acrylate, (a ) o-vinyloxymethylphenyl methyl acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, 2-(vinyloxyisopropoxy)ethyl (meth)acrylate, 2-(vinyloxyethoxy)propyl (meth)acrylate, 2-(vinyloxyethoxy)isopropyl (meth)acrylate, 2-(vinyloxyisopropyl)(meth)acrylate Oxy)propyl ester, 2-(vinyloxyisopropoxy)isopropyl (meth)acrylate, 2-(vinyloxyethoxyethoxy)ethyl (meth)acrylate, (methyl) ) 2-(vinyloxyethoxyisopropoxy) acrylate Ethyl ester, 2-(vinyloxyisopropoxyethoxy)ethyl (meth)acrylate, 2-(vinyloxyisopropoxyisopropoxy)ethyl (meth)acrylate, (A) 2-(vinyloxyethoxyethoxy)propyl acrylate, 2-(vinyloxyethoxyisopropoxy)propyl (meth)acrylate, 2-(ethylene) (meth)acrylate Oxypropoxyethoxypropyl)propyl ester, 2-(vinyloxyisopropoxyisopropoxy)propyl (meth)acrylate, 2-(vinyloxyethoxy)(meth)acrylate Ethoxy)isopropyl ester, 2-(vinyloxyethoxyisopropoxy)isopropyl (meth)acrylate, 2-(vinyloxyisopropoxyethoxy)(meth)acrylate Isopropyl ester, 2-(vinyloxyisopropoxyisopropoxy)isopropyl (meth)acrylate, 2-(vinyloxyethoxyethoxyethoxy)(meth)acrylate Ester, 2-(vinyloxyethoxyethoxyethoxyethoxy)ethyl (meth)acrylate, 2-(isopropoxyethoxy)ethyl (meth)acrylate, (A) 2-(isopropenyloxyethoxyethoxy)ethyl acrylate, 2-(isopropenyloxyethoxyethoxyethoxy)ethyl (meth)acrylate, (methyl) 2-(isopropenyloxyethoxyethoxyethoxyethoxy)ethylate, polyethylene glycol monovinyl ether (meth)acrylate, polypropylene glycol monovinyl ether (meth)acrylate Wait. Further, these compounds having a vinyl ether group and a (meth) acryloxy group may be used singly or in combination of two or more.

Among these compounds having a vinyl ether group and a (meth) propylene fluorenyloxy group, a compound represented by the above formula (3) is preferred, and 2-(vinyloxy ethoxy) (meth) acrylate is more preferred. ester. Further, a commercially available product of 2-(vinyloxyethoxy)ethyl (meth)acrylate may, for example, be VEEA as 2-(vinyloxyethoxy)ethyl acrylate or 2-methyl methacrylate. VEEM (manufactured by Nippon Shokubai) of (vinyloxyethoxy)ethyl ester or the like.

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

Other methods of introducing the structural unit (II-2) into the [A] polymer include, for example, using a polyfunctional (meth) acrylate as a monomer together with a monomer which provides the structural unit (I) or the like. A method of performing copolymerization or the like.

Examples of the polyfunctional (meth) acrylate include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, and triethylene glycol. Alcohol diacrylate, tetraethylene glycol di(meth)acrylate, tricyclodecyldidimethylene di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di Methyl) acrylate, tris(2-hydroxyethyl)isocyanurate tris(meth)acrylate, caprolactone modified tris(2-hydroxyethyl)isocyanurate Acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tris(A) Bis(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, bisphenol A diglycidyl ether, terminal (meth)acrylic acid adduct, 1,4- Butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, polyester di(methyl) Acrylate, polyethylene glycol II Acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, Lactone modified dipentaerythritol penta (meth) acrylate, di- Trimethylolpropane tetra(meth)acrylate, ethylene oxide modified bisphenol A di(meth)acrylate, propylene oxide modified bisphenol A di(meth)acrylate, ethylene oxide Modified hydrogenated bisphenol A di(meth)acrylate, propylene oxide modified hydrogenated bisphenol A di(meth)acrylate, ethylene oxide modified bisphenol F di(meth)acrylate, phenol novolac (meth) acrylate of phenol novolac polyglycidyl ether. Further, these monomers may be used alone or in combination of two or more.

Commercial products of the polyfunctional (meth) acrylate include, for example, SA1002 (manufactured by Mitsubishi Chemical Corporation), Viscoat 195, Viscoat 230, Viscoat 260, Viscoat 215, Viscoat 310, Viscoat 214HP, Viscoat 295, Viscoat 300, Viscoat 360, Viscoat GPT, Viscoat 400, Viscoat 700, Viscoat 540, Viscoat 3000, Viscoat 3700 (above manufactured by Osaka Organic Chemical Industry), KAYARAD R-526, KAYARAD HDDA, KAYARAD NPGDA, KAYARAD TPGDA, KAYARAD MANDA, KAYARAD R-551, KAYARAD R-712, KAYARAD R-604, KAYARAD R-684, KAYARAD PET-30, KAYARAD GPO-303, KAYARAD TMPTA, KAYARAD THE-330, KAYARAD DPHA, KAYARAD DPHA-2H, KAYARAD DPHA-2C, KAYARAD DPHA-2I, KAYARAD D-310, KAYARAD D-330, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARAD DN-0075, KAYARAD DN-2475, KAYARAD T-1420, KAYARAD T-2020, KAYARAD T-2040, KAYARAD TPA-320, KAYARAD TPA-330, KAYARAD RP-1040, KAYARAD RP-2040, KAYARAD R-011, KAYARAD R-300, KAYARAD R-205 (above manufactured by Nippon Kayaku), Aronix M-210, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-215, Aronix M-305, Aronix M- 309, Aronix M-310, Aronix M-315, Aronix M-325, Aronix M-400, Aronix M-6200, Aronix M-6400 (above manufactured by East Asia Synthetic), Light Acrylate BP-4EA, Light Acrylate BP-4PA , Light Acrylate BP-2EA, Light Acrylate BP-2PA, Light Acrylate DCP-A (above manufactured by Kyoeisha Chemical Co., Ltd.), New Frontier BPE-4, New Frontier BR-42M, New Frontier GX-8345 (above Industrial Pharmaceutical Manufacturing), ASF-400 (Nippon Steel Chemical Manufacturing), Ripoxy SP-1506, Ripoxy SP-1507, Ripoxy SP-1509, Ripoxy SP-4010, Ripoxy SP-4060, Ripoxy VR-77 (above by Showa Polymer manufacturing), NK Ester A-BPE-4 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

Among these polyfunctional (meth) acrylates, a compound having two or more (meth) acryloxy groups in the molecule and a compound having three or more (meth) acryloxy groups in the molecule are preferable. The compound having two or more (meth) propylene fluorenyl groups in the molecule is more preferably diethylene glycol di(meth) acrylate. Examples of the compound having three or more (meth) acryloxy groups in the molecule include a tri(meth) acrylate compound, a tetra (meth) acrylate compound, a penta (meth) acrylate compound, and a hexa Base) acrylate compound and the like. Among these compounds having three or more (meth) propylene fluorenyloxy groups, preferred is trimethylolpropane tri(meth) acrylate, ethylene oxide modified trimethylolpropane tri(meth) acrylate. Dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate.

The structural unit (II) preferably has two or more (meth) acryloxy groups. By having two or more (meth) acryloxy groups in the structural unit (II), more excellent sensitivity can be achieved, and an interlayer insulating film for display elements having excellent surface hardness, heat resistance, and the like can be formed.

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

[Structural unit (III)]

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

In the above formula (1), R ¹ is a hydrogen atom or a methyl group. R ² is an alkyl group, an alkenyl group, an alkynyl group or a decyloxyalkyl group having 6 to 30 carbon atoms or a crosslinked cyclic hydrocarbon group having 4 to 30 carbon atoms. Here, a part of the hydrogen atom of the alkyl group, the alkenyl group, the alkynyl group, the decyloxyalkyl group, and the crosslinked cyclic hydrocarbon group may be substituted with a hydroxyl group or a carboxyl group.

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

The alkyl group having 6 to 30 carbon atoms represented by the above R ² may, for example, be a linear or branched alkyl group having 6 to 30 carbon atoms, and specific examples thereof include a hexyl group, a heptyl group, an octyl group, a decyl group and a fluorenyl group. , undecyl, dodecyl, hexadecyl, stearyl, behenyl or the like. Among these alkyl groups, an alkyl group having 6 to 20 carbon atoms is preferable, an alkyl group having 10 to 20 carbon atoms is more preferable, and a dodecyl group, a hexadecyl group, and a stearyl group are particularly preferable.

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

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

Examples of the decyloxy group having 6 to 30 carbon atoms represented by the above R ² include, for example, lauryloxyethyl, lauryloxypropyl, stearyloxyethyl, stearyloxypropyl. , oleyloxyethyl, oleyloxypropyl and the like. Further, a group obtained by modifying a glycidyl group with oleic acid or a modified soybean oil fatty acid may be mentioned.

Examples of the crosslinked cyclic hydrocarbon group having 4 to 30 carbon atoms represented by the above R ² include norcaranyl (bicyclo[5.1.0]heptyl) and norpinanyl (bicyclo[3.1]. .0]heptyl), norbornyl (bicyclo[2.2.1]heptyl), adamantyl, bicyclo[2.2.2]octyl, bicyclo[3.2.1]octyl, tricyclo[2.2.1.0 ^{2 , 6} ] heptyl, tricyclo [5.2.1.0 ^2,6 ] fluorenyl, tricyclo [5.3.1.1 ^2,6 ] dodecyl, tricyclo[4.4.1.1 ^1,5 ]dodecyl, anthracene Alkyl, decyl, borneol, and the like. Among these groups, a crosslinked cyclic hydrocarbon group having 6 to 20 carbon atoms is preferable, and an adamantyl group or a tricyclo[5.2.1.0 ^2,6 ]fluorenyl group is more preferable.

Further, the crosslinked cyclic hydrocarbon group having 4 to 30 carbon atoms represented by the above R ² may further include a group obtained by condensing the rings of the ring exemplified above. Examples of the group in which the above-mentioned rings are condensed with each other include a group in which a crosslinked ring such as a norbornane ring is condensed with a polycyclic ring such as a monocyclic ring such as a cycloheptane ring or a cyclohexane ring or a decahydronaphthalene ring. In the case of a group having a shape in which the cross-linking rings are condensed with each other, examples of such a group include a group represented by the following formula.

Examples of the monomer which provides the structural unit (III) include hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, (methyl). Ethyl acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, cetyl methacrylate, stearyl methacrylate, docosane methacrylate a monomer containing a carbon number of 6 to 30 alkyl or a decyloxy group, such as a compound obtained by modifying oleic acid or soybean oil fatty acid, or a glycidyl methacrylate; (meth)acrylic acid; Naphthyl alkyl ester, norbornyl (meth)acrylate, norbornyl (meth)acrylate, adamantyl (meth)acrylate, bicyclo[2.2.2]octyl (meth)acrylate , (meth)acrylic bicyclo[3.2.1]octyl ester, (meth)acrylic acid tricyclo[2.2.1.0 ^2,6 ]heptyl ester, (meth)acrylic acid tricyclo[5.2.1.0 ^2,6 ]decyl ester , (meth)acrylic acid tricyclo [5.3.1.1 ^2,6 ] dodecyl ester, (meth)acrylic acid tricyclo [4.4.1.1 ^1,5 ] dodecyl ester, (meth) decyl methoxide Base ester, decyl (meth) acrylate, (A A monomer comprising a crosslinked cyclic hydrocarbon group having 4 to 30 carbon atoms, and the like. Among these monomers, lauryl methacrylate, adamantyl methacrylate, and stearyl methacrylate are preferable.

The content of the structural unit (III) in the polymer [A] is preferably 3 mol% or more and 50 mol% or less, more preferably 5 mol% or more, 50 mol% or less, and particularly preferably 10 mol%. More than %, 25% or less. By setting the content ratio of the structural unit (III) to the above range, the radiation sensitive composition can further promote the diffusion of acid and further improve the sensitivity.

[Other structural units]

The [A] polymer may have other structural units in addition to the structural unit (I), the structural unit (II), and the structural unit (III) within a range not impairing the effects of the present invention. Examples of the monomer which provides another structural unit include a monomer having a carboxyl group or a derivative thereof, a monomer having a hydroxyl group, and other monomers. Further, among these other structural units, the structural units included in the above structural unit (I) to structural unit (III) are not included.

Examples of the monomer having a carboxyl group or a derivative thereof include acrylic acid, methacrylic acid, crotonic acid, 2-propenyloxyethyl succinic acid, and 2-methyl propylene. Monocarboxylic acid such as methoxyethyl succinic acid, 2-propenyl methoxyethyl hexahydrophthalic acid, 2-methyl propylene oxyethyl hexahydrophthalic acid; maleic acid a dicarboxylic acid such as fumaric acid, citraconic acid, mesaconic acid or itaconic acid; an acid anhydride of the above dicarboxylic acid;

Examples of the monomer having a hydroxyl group include a hydroxyalkyl acrylate such as 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and 4-hydroxymethylcyclohexyl acrylate; 2-hydroxyethyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl methacrylate, 4-hydroxymethyl methacrylate A hydroxyalkyl methacrylate such as a cyclohexylmethyl ester or the like. Among these monomers having a hydroxyl group, from the viewpoint of heat resistance of the interlayer insulating film for a display device, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and methyl group are preferable. 2-hydroxyethyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxymethyl-cyclohexylmethyl acrylate, 4-hydroxymethyl-cyclohexylmethyl methacrylate.

Examples of the other monomer include alkyl acrylates such as methyl acrylate and isopropyl acrylate; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, and methacrylic acid. Alkyl methacrylate such as tert-butyl ester; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.0 ^2,6 ]non-8-yl acrylate, 2-(tricyclic) acrylate [5.2.1.0 ^2,6 ] 癸-8-yloxy)ethyl ester, isopropyl alicyclic alkyl ester such as isobornyl acrylate; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate , tricyclo [meth] acrylate [5.2.1.0 ^2,6 ] 癸-8-yl ester, 2-(tricyclo[5.2.1.0 ^2,6 ]non-8-yloxy)ethyl methacrylate, methyl A methacrylate alicyclic alkyl ester such as isobornyl acrylate; an aryl ester of acrylic acid such as phenyl acrylate or benzyl acrylate or an aralkyl ester of acrylic acid; phenyl methacrylate or benzyl methacrylate; An aryl ester of acrylic acid or an aralkyl group of methacrylic acid; a dialkyl dicarboxylate such as diethyl maleate, diethyl fumarate or diethyl itaconate Unsaturated five-membered ring methacrylate containing 1 atom of oxygen, such as tetrahydrofurfuryl methacrylate, tetrahydrofuranyl methacrylate, tetrahydropyran-2-methyl methacrylate or the like Cyclomethic acid; 4-methylpropenyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methylpropenyloxymethyl-2-methyl 2-isobutyl-1,3-dioxolane, 4-methylpropenyloxymethyl-2-cyclohexyl-1,3-dioxolan, 4-methylpropenyloxy 2-methyl-2-ethyl-1,3-dioxolane, 4-methylpropenyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolan An unsaturated heterocyclic 5-membered ring methacrylic acid containing 2 atomic oxygen; 4-propenyloxymethyl-2,2-dimethyl-1,3-dioxolan, 4-propenyloxy group 2-methyl-2-ethyl-1,3-dioxolane, 4-propenyloxymethyl-2,2-diethyl-1,3-dioxolane, 4-propene醯oxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-propenyloxymethyl-2-cyclopentyl-1,3-dioxolane, 4-propenyloxymethyl-2-cyclohexyl-1,3-dioxolan, 4-propenyloxyethyl-2-methyl-2-ethyl-1,3- Dioxolane, 4-propenyloxypropyl-2-methyl-2-ethyl-1,3-dioxolane, 4-propenyloxybutyl-2-methyl-2-ethyl Unsaturated five-membered ring acrylic acid containing 2-atomic oxygen such as styrene-1,3-dioxolane; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxy a vinyl aromatic compound such as styrene or 4-isopropenylphenol; N-phenyl maleimide, N-cyclohexyl maleimide, N-benzylbutylene Amine, N-butyl succinimide-3-synylene diimide benzoate, N-butyl succinimide -4- succinimide butyrate, N-butyl Dimethylene imino-6-maleimide hexanoate, N-butyl quinone imino-3-butanediimide propionate, N-(9-acridinyl) N-position substituted maleimide, such as maleimide, conjugated to 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene A diene compound; an unsaturated compound such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride or vinyl acetate.

Among these other monomers, from the viewpoint of copolymerization reactivity with the monomer having a carboxyl group or a derivative thereof, a monomer having a hydroxyl group, and developability of the radiation-sensitive composition, styrene is preferred. 4-isopropenylphenol, tricyclo[cyclopropyl] methacrylate [5.2.1.0 ^2,6 ]癸-8-yl ester, tetrahydrofurfuryl methacrylate, 1,3-butadiene, 4-propenyloxy Methyl-2-methyl-2-ethyl-1,3-dioxolane, N-cyclohexylmethyleneimine, N-phenyl maleimide, benzyl methacrylate ester.

The polystyrene-equivalent weight average molecular weight (Mw) of the [A] polymer by gel permeation chromatography (GPC) is preferably 2.0 × 10 ³ to 1.0 × 10 ⁵ , more preferably 5.0 × 10 ³ ~ 5.0 × 10 ⁴ . By setting the Mw of the [A] polymer to the above specific range, the sensitivity and alkali developability of the radiation sensitive composition can be improved.

The polystyrene-equivalent number average molecular weight (Mn) of the polymer obtained by GPC is preferably 2.0 × 10 ³ to 1.0 × 10 ⁵ , more preferably 5.0 × 10 ³ to 5.0 × 10 ⁴ . By setting the Mn of the [A] polymer to the above specific range, the curing reactivity at the time of curing of the coating film of the radiation sensitive composition can be improved.

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

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

Device: GPC-101 (made by Showa Denko)

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

Mobile phase: tetrahydrofuran

Column temperature: 40 ° C

Flow rate: 1.0 mL/min

Sample concentration: 1.0% by mass

Sample injection amount: 100 μL

Detector: differential refractometer

Reference material: monodisperse polystyrene

<[A] Synthesis Method of Polymer>

The [A] polymer can be produced, for example, by polymerizing a monomer corresponding to each predetermined structural unit in a suitable solvent by using a radical polymerization initiator. For example, it is preferably synthesized by a method in which a solution containing a monomer and a radical initiator is dropped into a solution containing a reaction solvent or a monomer to carry out a polymerization reaction; a solution containing a monomer and a radical are contained a method in which a solution of the initiator is dropped into a solution containing a reaction solvent or a monomer to carry out a polymerization reaction; a plurality of solutions containing various monomers and a solution containing a radical initiator are separately dropped to a reaction solvent or a single solvent A method of performing a polymerization reaction in a solution of a body.

The solvent to be used in the polymerization reaction of the polymer [A] is, for example, a solvent exemplified in the preparation of the radiation sensitive composition described later.

As the polymerization initiator used in the polymerization, an initiator which is generally known as a radical polymerization initiator can be used, and examples thereof include 2,2'-azobisisobutyronitrile and 2,2'-azobis. -(2,4-dimethylvaleronitrile), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2 -Azo compound such as methyl methacrylate; benzhydryl peroxide, lauryl peroxide, t-butyl peroxypivalate, 1,1'-bis-(third An organic peroxide such as oxidized cyclohexane; and hydrogen peroxide or the like.

In the polymerization reaction of [A] polymer, a molecular weight modifier may be used in order to adjust the molecular weight. Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, and third (dodecyl) mercaptan (tert-). Dodecyl mercaptan), thiol such as thioglycolic acid; xanthogenate such as dimethylxanthogen sulfide or diisopropyl xanthogen disulfide; oil Terpinolene, α-methylstyrene dimer, and the like.

<[B] Radiation-sensitive linear acid generator>

[B] The radiation sensitive acid generator is a compound which generates an acid due to irradiation of radiation. For example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, or the like can be used for the radiation. The radiation sensitive linear composition includes a [B] radiation sensitive acid generator, and the radiation sensitive linear composition can exhibit positive radiation characteristics.

[B] The radiation-sensitive linear acid generator may, for example, be an oxime sulfonate compound, a phosphonium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a hydrazine compound, a sulfonate compound, a carboxylic acid ester compound, or the like. . Further, these [B] sensitizing radioactive acid generators may be used alone or in combination of two or more.

[肟sulfonate compound]

The oxime sulfonate compound may, for example, be a compound containing an oxime sulfonate group represented by the following formula (4).

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

The linear or branched alkyl group represented by the above R ¹⁰ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The linear or branched alkyl group having 1 to 10 carbon atoms may be substituted, and examples of the substituent include an alkoxy group having 1 to 10 carbon atoms and 7,7-dimethyl-2-oxorone norbornene. The base or the like contains an alicyclic group having a bridged alicyclic group and the like. Further, a preferred alicyclic group is a bicycloalkyl group. The aryl group represented by the above R ¹⁰ is preferably an aryl group having 6 to 11 carbon atoms, and more preferably a phenyl group or a naphthyl group. The aryl group may be substituted, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

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

In the above formula (5), R ¹⁰ has the same meaning as the above formula (4). X is an alkyl group, an alkoxy group, or a halogen atom. r is an integer from 0 to 3. However, when there are a plurality of Xs, a plurality of Xs may be the same or different.

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

The oxime sulfonate compound represented by the above (5) is, for example, a compound represented by the following formula (5-1) to formula (5-5).

[化8]

The above compound (5-1) (5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, compound (5-2) (5-octyl) Sulfosinoxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, compound (5-3) (camphorsulfonyloxyimino-5H-thiophene-2 -ylidene-(2-methylphenyl)acetonitrile, compound (5-4) (5-p-toluenesulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylbenzene Acetonitrile and compound (5-5) (5-octylsulfonyloxyimino)-(4-methoxyphenyl)acetonitrile are commercially available Products to get.

[鎓盐]

Examples of the onium salt include a diphenylphosphonium salt, a triphenylsulfonium salt, a phosphonium salt, a benzothiazolium salt, and a tetrahydrothiophene salt.

Examples of the diphenylphosphonium salt include diphenylphosphonium tetrafluoroborate, diphenylphosphonium hexafluorophosphonate, diphenylphosphonium hexafluoroarsenate, diphenylsulfonium trifluoromethanesulfonate, and Phenylfluorene trifluoroacetate, diphenylphosphonium-p-toluenesulfonate, diphenylphosphonium butyl tris(2,6-difluorophenyl)borate, 4-methoxyphenylphenylphosphonium tetra Fluoroborate, bis(4-t-butylphenyl)phosphonium tetrafluoroborate, bis(4-t-butylphenyl)phosphonium hexafluoroarsenate, bis(4-tert-butylphenyl)錪Trifluoromethanesulfonate, bis(4-t-butylphenyl)phosphonium trifluoroacetate, bis(4-t-butylphenyl)phosphonium-p-toluenesulfonate, double (4-third Butylphenyl) camphorsulfonic acid and the like.

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

Examples of the onium salt include an alkyl phosphonium salt, a benzyl phosphonium salt, a dibenzyl phosphonium salt, a substituted benzyl phosphonium salt, and the like.

Examples of the alkyl phosphonium salt include 4-ethyloxyphenyl dimethyl hexafluoroantimonate, 4-ethyl methoxy phenyl dimethyl hexafluoro arsenate, and dimethyl-4-. (Benzyloxycarbonyloxy)phenylphosphonium hexafluoroantimonate, dimethyl-4-(benzylideneoxy)phenylphosphonium hexafluoroantimonate, dimethyl-4-(benzonitrile) Phenyl hydrazine hexafluoroarsenate, dimethyl-3-chloro-4-ethoxylated phenyl hexafluoroantimonate, and the like.

Examples of the benzyl sulfonium salt include benzyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate, and 4-ethenyloxyphenylbenzyl chloride. Methyl hydrazine hexafluoroantimonate, benzyl-4-methoxyphenylmethyl hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethyl hexafluoroantimonate Benzyl-3-chloro-4-hydroxyphenylmethylphosphonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate, and the like.

Examples of the dibenzyl sulfonium salt include dibenzyl-4-hydroxyphenylphosphonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylphosphonium hexafluorophosphate, and 4-ethyloxyphenyl dibenzylate. Hexafluoroantimonate, dibenzyl-4-methoxyphenylphosphonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylphosphonium hexafluoroarsenate, dibenzyl- 3-methyl-4-hydroxy-5-t-butylphenylphosphonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylphosphonium hexafluorophosphate, and the like.

Examples of the substituted benzyl phosphonium salt include p-chlorobenzyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate and p-nitrobenzyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate. p-Chlorobenzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, 3,5-dichlorobenzyl 4--4-hydroxyphenylmethyl hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethyl hexafluoroantimonate, and the like.

Examples of the benzothiazolium salt include 3-benzylbenzothiazolium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluorophosphate, 3-benzylbenzothiazolium tetrafluoroborate, and 3 -(p-methoxybenzyl)benzothiazolium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazolium hexafluoroantimonate, 3-benzyl-5-chlorobenzoate Thiazol hexafluoroantimonate and the like.

Examples of the tetrahydrothiophene sulfonium salt include 4,7-di-n-butoxy-1-naphthyltetrahydrothiophene trifluoromethanesulfonate and 1-(4-n-butoxynaphthalen-1-yl). Tetrahydrothiophene trifluoromethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene nonafluoro-n-butanesulfonate, 1-(4- n-Butoxynaphthalen-1-yl)tetrahydrothiophene-1,1,2,2-tetrafluoro-2-(norborn-2-yl)ethanesulfonate, 1-(4-n-butoxy Naphthyl-1-yl)tetrahydrothiophene-2-(5-tert-butoxycarbonyloxybicyclo[2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethyl Sulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene-2-(6-t-butoxycarbonyloxybicyclo[2.2.1]heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, and the like.

[sulfonimide compound]

Examples of the sulfonimide compound include N-(trifluoromethylsulfonyloxy)butaneimine, N-(camphorsulfonyloxy)butadienimide, and N-(4-methylbenzene). Sulfosulfonyloxy)butanediamine, N-(2-trifluoromethylphenylsulfonyloxy)butanediamine, N-(4-fluorophenylsulfonyloxy)butane Imine, N-(trifluoromethylsulfonyloxy) phthalimide, N-(camphorsulfonyloxy) phthalimide, N-(2-trifluoromethylbenzene Alkyl sulfonyloxy) phthalimide, N-(2-fluorophenylsulfonyloxy) phthalimide, N-(trifluoromethylsulfonyloxy)diphenyl Maleimide, N-(camphorsulfonyloxy)diphenylmethylene iodide, 4-methylphenylsulfonyloxy)diphenylbutyleneimine, N-(2-trifluoromethylphenylsulfonyloxy)diphenylmethylene iodide, N-(4-fluorophenylsulfonyloxy)diphenylmethyleneimine , N-(4-fluorophenylsulfonyloxy)diphenylmethylene iodide, N-(phenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3 -Dicarboxy quinone imine, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(three Fluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-(nonafluorobutsulfonyloxy)bicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine, N-(camphorsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-( camphor sulfonate) -7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(three Fluoromethylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(4-methylphenylsulfonyloxy)bicyclic [2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-(4-methylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2-trifluoromethylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-(4-fluorobenzene Alkylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-(4-fluorophenylsulfonyloxy)-7-oxabicyclo[2.2. 1]hept-5-ene-2,3-dicarboxy quinone imine, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxo-2,3-di Carboxylimine, N-(camphorsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyindenine, N-(4-methylphenylsulfonate Oxy)bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxy quinone imine, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1] Heptane-5,6-oxo-2,3-dicarboxyindenine, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxo-2,3 -Dicarboxy quinone imine, N-(trifluoromethyl) Alkyl sulfonyloxy)naphthyldicarboxy quinone imine, N-(camphorsulfonyloxy)naphthyldicarboxy quinone imine, N-(4-methylphenylsulfonyloxy)naphthyldicarboxyanthracene Imine, N-(phenylsulfonyloxy)naphthyldicarboxy quinone imine, N-(2-trifluoromethylphenylsulfonyloxy)naphthyldicarboxy quinone imine, N-(4- Fluorophenylsulfonyloxy)naphthyldicarboxyarsenine, N-(pentafluoroethylsulfonyloxy)naphthyldicarboxyanilide, N-(heptafluoropropylsulfonyloxy)naphthyl Dicarboxy quinone imine, N-(nonafluorobutylsulfonyloxy)naphthyl dicarboxy quinone imine, N-(ethylsulfonyloxy)naphthyl dicarboxy quinone imine, N-(propyl sulfonate醯oxy)naphthyldicarboxy quinone imine, N-(butylsulfonyloxy)naphthyldicarboxy quinone imine, N-(pentylsulfonyloxy)naphthyldicarboxy quinone imine, N- (hexylsulfonyloxy)naphthyldicarboxyanilide, N-(heptylsulfonyloxy)naphthyldicarboxyfluorene An amine, N-(octylsulfonyloxy)naphthyldicarboxy quinone imine, N-(decylsulfonyloxy)naphthyldicarboxy quinone imine, and the like.

[halogen-containing compound]

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

[diazomethane compounds]

Examples of the diazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, and bis(p-toluene). Disulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, bis(p-chlorophenylsulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonate Base heavy nitrogen methane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, phenylsulfonate Sulfhydryl (benzhydryl) diazomethane and the like.

[碸 compound]

Examples of the ruthenium compound include a β-ketooxime compound, a β-sulfonylhydrazine compound, and a diaryldiamine compound.

[sulfonate compound]

Examples of the sulfonate compound include an alkylsulfonate, a halogenated alkylsulfonate, an arylsulfonate, and an imidosulfonate.

[Carboxylic acid ester compound]

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

The [B] sensitizing radioactive acid generator is preferably an oxime sulfonate compound, a phosphonium salt or a sulfonate compound from the viewpoint of sensitivity and solubility. Oxime sulfonate compound The compound represented by the above formula (4) is more preferable, and the compound represented by the above formula (5) is more preferable, and the compound represented by the above formula (5-1) which can be obtained as a commercial product is particularly preferable. The onium salt is preferably a tetrahydrothiophene salt or a benzyl phosphonium salt, more preferably 4,7-di-n-butoxy-1-naphthyltetrahydrothiophene trifluoromethanesulfonate, benzyl-4-hydroxyl Phenylmethyl sulfonium hexafluorophosphate. The sulfonate compound is preferably a haloalkyl sulfonate, more preferably N-hydroxynaphthalene imine-triflate.

The content of the [B] radiation-sensitive acid generator in the radiation sensitive composition is preferably 0.1 parts by mass to 10 parts by mass, more preferably 1 part by mass to 5 parts by mass, per 100 parts by mass of the [A] polymer. . By setting the content of the [B] sensitizing radioactive acid generator to the above specific range, the sensitivity of the radiation sensitive composition can be optimized, and interlayer insulation for a display element which maintains transparency and has high surface hardness can be formed. membrane.

<[C] compound>

The [C] compound is a compound having a molecular weight of 1,000 or less and containing one or more (meth) acrylonitrile groups. The radiation sensitive composition can further improve the sensitivity by containing the [C] compound, and can improve the surface hardness, heat resistance, solvent resistance, voltage holding ratio, and the like of the cured film such as the interlayer insulating film for a display element to be formed. .

The compound [C] is not particularly limited as long as it is a compound containing at least one (meth) acryloyl group in the molecule. Examples of the compound having one (meth) acryl fluorenyl group include acrylamide, (meth) acryl hydrazinomorph, (meth) acrylate 7-amino-3,7-dimethyloctyl ester, Isobutoxymethyl (meth) acrylamide, isobornyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyl Diethylene glycol (meth) acrylate, third octyl (meth) acrylamide, diacetone (Meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentadiene (methyl) Acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, N,N-dimethyl(meth)acrylamide, tetrachlorophenyl (methyl) Acrylate, 2-tetrachlorophenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, tetrabromophenyl (meth)acrylate, 2-tetrabromophenoxy (meth)acrylate Ethyl ethyl ester, 2-trichlorophenoxyethyl (meth)acrylate, tribromophenyl (meth)acrylate, 2-tribromophenoxyethyl (meth)acrylate, (meth)acrylic acid 2 -hydroxyethyl ester, 2-hydroxypropyl (meth)acrylate, vinyl caprolactam, N-vinylpyrrolidone, phenoxyethyl (meth)acrylate, butoxy (meth)acrylate Ethyl ester, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (meth) acrylate Anthracene ester, methyl tri-ethyl diglycol (meth) acrylate, and the like. Among these compounds having one (meth)acryl fluorenyl group, isobornyl (meth)acrylate, lauryl (meth)acrylate, and phenoxyethyl (meth)acrylate are preferable. Commercial products of these compounds include, for example, Aronix M-101, Aronix M-102, Aronix M-111, Aronix M-113, Aronix M-117, Aronix M-152, Aronix TO-1210 (above manufactured by East Asia Synthetic Co., Ltd.) ), KAYARAD TC-110S, KAYARAD R-564, KAYARAD R-128H (above manufactured by Nippon Kayaku), Viscoat 192, Viscoat 220, Viscoat 2311HP, Viscoat 2000, Viscoat 2100, Viscoat 2150, Viscoat 8F, Viscoat 17F (above) Made by Osaka Organic Chemical Industry).

Examples of the compound containing two or more (meth) acryloyl fluorenyl groups include: Alcohol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, triethylene glycol diacrylate, tetraethylene glycol di(meth)acrylate, tricyclodecadenyl dimethylene Di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tris(meth)acrylic acid Ester, caprolactone modified tris(2-hydroxyethyl)isocyanurate tris(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide (hereinafter referred to as "EO") modified trimethylolpropane tri(meth)acrylate, propylene oxide (hereinafter referred to as "PO") modified trimethylolpropane tri(meth)acrylate, tripropylene glycol di(a) Bis(meth)acrylate, neopentyl glycol di(meth)acrylate, bisphenol A diglycidyl ether, two-terminal (meth)acrylic acid adduct, 1,4-butanediol di(meth)acrylate 1,6-hexanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, polyester di(meth)acrylate, polyethylene glycol II ( Methyl) acrylate, dipentaerythritol hexa(methyl) propyl Acid ester, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol penta (methyl) Acrylate, di-trimethylolpropane tetra(meth)acrylate, EO modified bisphenol A di(meth)acrylate, PO modified bisphenol A di(meth)acrylate, EO modified hydrogenation Bisphenol A di(meth)acrylate, PO modified hydrogenated bisphenol A di(meth)acrylate, EO modified bisphenol F di(meth)acrylate, phenol novolac polyglycidyl ether Base) acrylate and the like. Commercial products of these compounds containing two or more (meth) acrylonitrile groups include, for example, SA1002 (manufactured by Mitsubishi Chemical Corporation), Viscoat 195, Viscoat 230, Viscoat 260, Viscoat 215, Viscoat 310, Viscoat 214HP, Viscoat 295, Viscoat 300, Viscoat 360, Viscoat GPT, Viscoat 400, Viscoat 700, Viscoat 540, Viscoat 3000, Viscoat 3700 (above manufactured by Osaka Organic Chemical Industry), KAYARAD R-526, KAYARAD HDDA, KAYARAD NPGDA, KAYARAD TPGDA, KAYARAD MANDA, KAYARAD R-551, KAYARAD R-712, KAYARAD R-604, KAYARAD R-684, KAYARAD PET-30, KAYARAD GPO-303, KAYARAD TMPTA, KAYARAD THE-330, KAYARAD DPHA, KAYARAD DPHA-2H, KAYARAD DPHA-2C, KAYARAD DPHA-2I, KAYARAD D-310 , KAYARAD D-330, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARAD DN-0075, KAYARAD DN-2475, KAYARAD T-1420, KAYARAD T-2020, KAYARAD T-2040 , KAYARAD TPA-320, KAYARAD TPA-330, KAYARAD RP-1040, KAYARAD RP-2040, KAYARAD R-011, KAYARAD R-300, KAYARAD R-205 (above manufactured by Nippon Kayaku), Aronix M-210, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-215, Aronix M-305, Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-325, Aronix M-400, Aronix M-6200, Aronix M-6400 (above manufactured by East Asia Synthetic), Light Acrylate BP-4EA, Light Acrylate BP-4PA Light Acrylate BP-2EA, Light Acrylate BP-2PA, Light Acrylate DCP-A (above manufactured by Kyoeisha Chemicals), New Frontier BPE-4, New Frontier BR-42M, New Frontier GX-8345 (above by the first industry) Pharmaceutical manufacturing), ASF-400 (Nippon Steel Chemical Manufacturing), Ripoxy SP-1506, Ripoxy SP-1507, Ripoxy SP-1509, Ripoxy VR-77, Ripoxy SP-4010, Ripoxy SP-4060 (manufactured by Showa Polymer), NK Ester A-BPE-4 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and the like.

Among these compounds, a compound containing at least two (meth)acryl fluorenyl groups in the molecule is preferable, and a compound containing at least three (meth) acryl fluorenyl groups in the molecule is more preferable. Such a compound containing at least three (meth)acryl fluorenyl groups in the molecule can be derived from the above-exemplified tri(meth)acrylate compound, tetra(meth)acrylate compound, penta(meth)acrylate compound, A hexa(meth) acrylate compound or the like is selected.

Among these compounds, the compound [C] is particularly preferably a compound having the following skeleton: a skeleton derived from a diol structure having a carbon number of 2 to 12 represented by the following formula (6), and a derivative represented by the formula (7) The skeleton of hydroxymethylpropane, the skeleton derived from pentaerythritol represented by formula (8), or the skeleton derived from dipentaerythritol represented by formula (9).

In the above formula (6), n is an integer of 2 to 12.

Such a preferred [C] compound is exemplified by trimethylolpropane tri(methyl). Acrylate, EO modified trimethylolpropane tri(meth) acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, di-trimethylolpropane tetra (methyl) Acrylate, ethylene oxide modified dipentaerythritol hexaacrylate, propylene oxide modified dipentaerythritol hexaacrylate, ε-caprolactone modified dipentaerythritol hexaacrylate, succinic acid modified pentaerythritol triacrylate, etc. . Further, in the radiation-sensitive composition, the [C] compounds may be used alone or in combination of two or more. Further, the [C] compound is a compound having a molecular weight of 1,000 or less.

The content of the [C] compound in the radiation-sensitive composition is preferably 1% by mass or more and 50% by mass or less, more preferably 1% by mass or more and 30% by mass or less, and particularly preferably 1% by mass in terms of solid content. The above is 20% by mass or less. By setting the content of the [C] compound in the radiation-sensitive composition to the above range, it is possible to further improve the surface hardness, solvent resistance, heat resistance, and voltage retention of the cured film such as the interlayer insulating film for a display element to be formed. rate.

<Other optional components>

The radiation sensitive composition may contain a sensitizer or an alkalinity in addition to the [A] polymer, the [B] radiation sensitive acid generator, and the [C] compound, within a range that does not impair the effects of the present invention. Other optional components such as a compound, a surfactant, a adhesion aid, a compound having a hindered phenol structure, and the like. In addition, each component may be used alone or in combination of two or more. Hereinafter, each component will be described in detail.

[sensitizer]

The radiation sensitive composition preferably further contains a sensitizer as an appropriate component. The sensitizing radioactive composition further contains a sensitizer, which can further improve the Sensing the sensitivity of the radioactive composition. The sensitizer absorbs active light or radiation to become an electronically excited state. The sensitizer that is in an electronically excited state is brought into contact with the photoacid generator to cause electron transfer, energy transfer, heat generation, and the like, whereby the [B] sensitizing radioactive acid generator chemically changes to decompose and generate an acid.

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

Examples of the sensitizer include pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7. Polynuclear aromatics such as dimethoxy oxime, 9,10-dipropyloxyanthracene; fluorescein, eosin, erythrosine, rhodamine B ), rose bengal, etc. xanthene; xanthone, thioxanthone, dimethyl thioxanthone, diethyl thioxanthone, isopropyl thiophene Oxanthone such as ketone; thiacarbocyanine, oxacarbocyanine, etc.; merocyanine, carbomerocyanine, etc. ; rhodacyanine; oxonol; thionine, methylene blue, toluidine blue Thiazines such as toluidine blue; acridines such as acridine orange, chloroflavin, and acriferlavin; acridone, 10-butyl Acridine ketones such as -2-chloroacridone; anthraquinones such as anthraquinone; squarylium squarylium; squarylium; styryl; 2-[ Basic base-styryl such as 2-[4-(dimethylamino)phenyl]vinyl]benzoxazole; 7-diethylamino 4-methylcoumarin, 7-Hydroxy 4-methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H,5H,11H[1]benzopyrano[6.7.8-ij]quinolidazine- 11-ketone and other coumarins.

Among these [C] sensitizers, polycyclic aromatics, xanthone, acridone, styryl, basic styryl, coumarin, and more preferably polycyclic aromatic are preferable. The group, xanthones, particularly preferably 9,10-dibutoxyanthracene, isopropylthioxanthone.

The content of the sensitizer in the radiation sensitive composition is preferably 0.1 parts by mass to 10 parts by mass, and more preferably 0.5 parts by mass to 5 parts by mass, per 100 parts by mass of the [A] polymer. By setting the content of the sensitizer to the above range, the sensitivity can be further improved.

[alkaline compound]

The basic compound can be any of the compounds used in the chemical amplification resist For the selection, for example, an aliphatic amine, an aromatic amine, a heterocyclic amine, a quaternary ammonium hydroxide, a quaternary ammonium carboxylic acid salt or the like can be given. By including the basic compound in the radiation-sensitive composition, the diffusion length of the acid generated from the [B] sensitizing radioactive acid generator by exposure can be appropriately controlled, and the pattern developability can be improved.

Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, and tri-n-pentylamine. Diethanolamine, 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, and N-methyl. 4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine Nicotine), nicotinic acid, nicotinic acid amide, quinoline, 8-oxyquinoline, pyrazine, pyrazole, pyridazine (pyridazine), purine, pyrrolidine, piperididine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo[4.3.0] -5-decene, 1,8-diazabicyclo[5.3.0]-7-undecene, and the like.

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

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

Among these basic compounds, a heterocyclic amine is preferred, and more preferred is 4-dimethylaminopyridine, 4-methylimidazole, 1,5-diazabicyclo[4,3,0]-5-fluorene. Alkene.

The content of the basic compound in the radiation sensitive composition is preferably 0.001 parts by mass to 1 part by mass, and more preferably 0.005 parts by mass to 0.2 parts by mass, based on 100 parts by mass of the [A] polymer. By setting the content of the basic compound to the above specific range, the pattern developability is further improved.

[Surfactant]

The surfactant can further improve the coating film formability of the radiation sensitive composition. Examples of the surfactant include a fluorine-based surfactant and an anthrone-based surfactant. By including the surfactant in the radiation-sensitive composition, the surface smoothness of the coating film can be improved, and as a result, the film thickness uniformity of the interlayer insulating film for a display element can be further improved.

The fluorine-based surfactant is preferably a compound having a fluoroalkyl group and/or a fluorine-extended alkyl group at at least any one of a terminal group, a main chain and a side chain, and examples thereof include 1,1,2,2-tetrafluoro-n-octyl group. (1,1,2,2-tetrafluoro-n-propyl)ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl)ether, hexaethylene glycol di(1,1,2,2 , 3,3-hexafluoro-n-pentyl)ether, octaethylene glycol bis(1,1,2,2-tetrafluoro-n-butyl)ether, hexapropanediol bis (1,1,2,2,3,3 -hexafluoro-n-pentyl)ether, octapropylene glycol bis(1,1,2,2-tetrafluoro-n-butyl)ether, sodium perfluoro-n-dodecanesulfonate, 1,1,2,2,3,3 -hexafluoro-n-decane, 1,1,2,2,3,3,9,9,10,10-decafluoro-n-dodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, halothane Sodium carboxylate, diglycerol tetrakis(fluoroalkylpolyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyl Ethanol, perfluoroalkyl alkoxylate, fluoroalkyl carboxylate Wait.

Examples of commercially available fluorine-based surfactants include BM-1000 and BM-1100 (above, manufactured by BM Chemie), Megafac F142D, Megafac F172, Megafac F173, Megafac F183, Megafac F178, and Megafac F191. Megafac F471, Megafac F476 (above manufactured by Dainippon Ink Chemical Industry), Fluorad FC-170C, Fluorad FC-171, Fluorad FC-430, Fluorad FC-431 (above manufactured by Sumitomo 3M), Surflon S-112, Surflon S -113, Surflon S-131, Surflon S-141, Surflon S-145, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC -106 (above manufactured by Asahi Glass), Eftop EF301, Eftop EF303, Eftop EF352 (above manufactured by New Akita Chemicals), Ftergent FT-100, Ftergent FT-110, Ftergent FT-140A, Ftergent FT-150, Ftergent FT-250 Ftergent FT-251, Ftergent FT-300, Ftergent FT-310, Ftergent FT-400S, Ftergent FTX-218, Ftergent FT-251 (above manufactured by Neos), and the like.

Examples of the anthrone-based surfactants include Toray Silicone DC3PA, Toray Silicone DC7PA, Toray Silicone SH11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH-190, Toray Silicone SH-193, Toray Silicone SZ-6032, Toray Silicone SF-8428, Toray Silicone DC-57, Toray Silicone DC-190, SH 8400 FLUID (above manufactured by Toray Dow Corning Silicone), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (the above is manufactured by GE Toshiba Anthrone), an organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

The content of the surfactant in the radiation sensitive composition is preferably 0.01 parts by mass or more and 2 parts by mass or less, and more preferably 0.05 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass of the [A] polymer. By setting the content of the surfactant to the above specific range, the film thickness uniformity of the coating film can be further improved.

[Close Agent]

In order to improve the adhesion to the inorganic substance to be a substrate, for example, an anthrone compound such as anthrone, fluorenone or fluorenone, or a metal such as gold, copper or aluminum and an insulating film, an adhesion aid may be used. The adhesion aid is preferably a functional decane coupling agent. Examples of the functional decane coupling agent include a decane coupling agent having a reactive substituent such as a carboxyl group, a methacryl fluorenyl group, an isocyanate group, an epoxy group (preferably an oxiran group), or a thiol group.

Examples of the functional decane coupling agent include trimethoxydecyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, and γ- Isocyanate propyl triethoxy decane, γ-glycidoxypropyl trimethoxy decane, γ-glycidoxypropyl alkyl dialkoxy decane, γ-chloropropyl trialkoxy decane, Γ-mercaptopropyltrialkoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. Among these compounds, preferred are γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropylalkyldialkoxydecane, and β-(3,4-epoxycyclohexyl)ethyltrimethyl. Oxydecane, γ-methyl propyl Isomethoxypropyltrimethoxydecane.

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

[Compound with hindered phenol structure]

A compound having a hindered phenol structure is a component for preventing cracking of a bond of a compound caused by a radical or a peroxide. The compound having a hindered phenol structure includes, in addition to the compound having a hindered phenol structure, a radical scavenger such as a compound having a hindered amine structure.

Examples of the compound having a hindered phenol structure include pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] and thiodiethylidene bis[3-(3). , 5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, Tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di -T-butyl-4-hydroxybenzyl)benzene, N,N'-hexane-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenylpropane Indoleamine, 3,3',3',5',5'-hexa-t-butyl-a,a',a'-(mesitylene-2,4,6-triyl)tri-pair Cresol, 4,6-bis(octylthiomethyl)-o-cresol, 4,6-bis(dodecylthiomethyl)-o-cresol, exoethyl bis(oxyethylene) double [3] -(5-t-butyl-4-hydroxy-m-tolyl)propionate, hexamethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate ], 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazine-2,4,6 (1H , 3H, 5H) - three Ketone, 2,6-di-t-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamine)phenol, and the like.

Examples of the compound having a hindered amine structure include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate and bis(2,2,6,6-tetramethyl- 4-piperidinyl) succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(N-octyloxy-2,2, 6,6-tetramethyl-4-piperidinyl) sebacate, bis(N-benzyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, Bis(N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4- Piperidinyl)-2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(1-propenylfluorenyl-2,2,6,6 -tetramethyl-4-piperidinyl)-2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)-2-butylmalonate, bis (1,2 , 2,6,6-pentamethyl-4-piperidinyl) sebacate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4-[3-( 3,5-di-t-butyl-4-hydroxyphenyl)propanoxy]-1-[2-(3-(3,5-di-t-butyl-4-hydroxyphenyl)propane醯oxy)ethyl]-2,2,6,6-tetramethylpiperidine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino -N-(2,2,6,6-tetramethyl-4-piperidyl)propanamide, tetrakis(2,2,6,6-tetramethyl-4-piperidinyl) 1,2, 3,4-Ding Tetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylic acid ester compound.

The content of the compound having a hindered phenol structure in the radiation sensitive composition is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 1.5 parts by mass or more and 3 parts by mass based on 100 parts by mass of the [A] polymer. the following. By setting the content of the compound having a hindered phenol structure to the above specific range, not only the sensitivity of the radiation sensitive composition but also the voltage holding ratio of the interlayer insulating film for a display element to be formed can be further improved.

<Preparation method of radiation sensitive composition>

The radiation sensitive composition is prepared by dissolving or dispersing a [A] polymer, [B] a radioactive acid generator, a [C] compound, and optionally any other components in a solvent. The radiation sensitive composition can be prepared, for example, by mixing the components in a predetermined ratio in a solvent.

As the solvent, a compound which uniformly dissolves or disperses each component and does not react with each component is suitably used. Examples of the solvent include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, and propylene glycol singles. Alkyl ether propionate, aromatic hydrocarbons, ketones, other esters, and the like.

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

Examples of the ethers include tetrahydrofuran and the like.

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

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

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

Examples of the aromatic hydrocarbons include toluene and xylene.

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, and 2-hydroxy-2- Ethyl methacrylate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, 3-hydroxypropyl Ethyl acetate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, methoxy Propyl propyl acetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, propoxy Ethyl acetate, propyl propyl acetate, butyl propyl acetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, 2-methoxy Methyl propyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxy Ethyl propyl propionate, propyl 2-ethoxypropionate, 2-B Butyl propyl propionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, 3-methoxy Methyl propionate, 3-methoxy

Ethyl propionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxyl Propyl propionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propoxy Butyl propionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, and the like.

Among these solvents, preferred are ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, butyl methoxyacetate, and more preferably two. Ethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl methoxyacetate.

<Method of Forming Interlayer Insulation Film for Display Element>

The radiation sensitive linear composition is suitable as an interlayer insulating film for a display element Form the material. Further, the present invention also suitably includes an interlayer insulating film for a display element formed of the radiation sensitive composition.

A method of forming an interlayer insulating film for a display element of the present invention includes:

(1) Step of forming a coating film on a substrate using the radiation-sensitive composition (hereinafter also referred to as "step (1)"); (2) a step of irradiating at least a part of the coating film with radiation (hereinafter also referred to as "step (2)"); (3) the above-mentioned irradiation of radiation The step of developing the coating film (hereinafter also referred to as "step (3)"); and (4) the step of heating the above-described coating film (hereinafter also referred to as "step (4)").

According to this formation method, it is possible to form an interlayer insulating film for a display element which is excellent in surface hardness, solvent resistance, heat resistance, and voltage holding ratio. In addition, by using the radiation-sensitive composition having excellent sensitivity, it is possible to easily form an interlayer insulating film for a display element having a fine and delicate pattern. Therefore, the formed interlayer insulating film for a display element 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 radiation sensitive composition is applied onto a substrate to form a coating film. It is preferred to remove the solvent by prebaking the coated surface.

Examples of the substrate include glass, quartz, anthrone, and a resin. Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, polyamidimide, a ring-opening polymer of a cyclic olefin, and a hydrogenated product thereof. The pre-baking conditions vary depending on the type of each component, the blending ratio, and the like, and can be set to 70 ° C to 120 ° C for about 1 minute to 10 minutes.

[Step (2)]

In this step, at least a part of the formed coating film is irradiated with radiation to perform exposure. At the time of exposure, exposure is usually performed through a photomask having a predetermined pattern. The radiation for exposure is preferably radiation having a wavelength in the range of 190 nm to 450 nm, and more preferably radiation containing ultraviolet rays of 365 nm. The exposure amount is a value obtained by measuring the intensity at a wavelength of 365 nm of the radiation using an illuminometer (OAI model 356, manufactured by OAI Optical Associates), and is preferably 500 J/m ² to 6,000 J/m ² . More preferably, it is 1,500 J/m ² -1,800 J/m ² .

[Step (3)]

In this step, the coating film irradiated with radiation is developed. By developing the exposed coating film, an unnecessary portion (irradiated portion of the radiation) is removed to form a predetermined pattern. The developer used in the developing step is preferably an alkaline aqueous solution. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and amine; and quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide.

A sufficient amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the aqueous alkali solution. 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 obtaining appropriate developability. Examples of the development method include a puddle method, a dipping method, a shaking dipping method, and a shower method. The development time varies depending on the composition of the radiation-sensitive composition, and is about 10 seconds to 180 seconds. Following this development treatment, a desired pattern can be formed by performing, for example, running water cleaning for 30 seconds to 90 seconds, followed by air drying using, for example, compressed air or compressed nitrogen.

[Step (4)]

In this step, the developed coating film described above is heated. When heating, the patterned film is heated by using a heating means such as a hot plate or an oven to promote the hardening 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 machine, for example, about 5 minutes to 30 minutes on the hot plate and about 30 minutes to 90 minutes in the oven. In addition, it is also possible to use staged baking in which the heating step is performed twice or more. Law and so on. In this manner, the pattern-shaped film corresponding to the target interlayer insulating film for display elements can be formed on the surface of the substrate. Further, the use of the cured film is not limited to the interlayer insulating film for display elements, and may be used as a spacer or a protective film.

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

[Examples]

Hereinafter, the present invention will be described in detail based on the examples, but the present invention is not limited by the examples.

<[A] Synthesis of Polymers>

[Synthesis Example 1]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were added. Next, 50 parts by mass of tetrahydropyranyl methacrylate providing the structural unit (I), 35 parts by mass of glycidyl methacrylate providing the structural unit (II), and methacrylic acid providing the structural unit (III) 5 parts by mass of the lauryl ester, and 10 parts by mass of methacrylic acid and 31 parts by mass of the α-methylstyrene dimer which provided another structural unit were slowly stirred after nitrogen substitution. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-1). The Mw of the copolymer (A-1) was 9,000. Further, the solid content concentration of the polymer solution obtained here was 32.1% by mass.

[Synthesis Example 2]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were added. Next, 50 parts by mass of tetrahydropyranyl methacrylate providing the structural unit (I), 20 parts by mass of glycidyl methacrylate providing the structural unit (II), and methacrylic acid providing the structural unit (III) 20 parts by mass of the lauryl ester, and 10 parts by mass of methacrylic acid and 3 parts by mass of the α-methylstyrene dimer which provided another structural unit were slowly stirred after nitrogen substitution. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-2). The Mw of the copolymer (A-2) was 8,000. Further, the solid content concentration of the polymer solution obtained here was 31.5% by mass.

[Synthesis Example 3]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were added. Next, 50 parts by mass of tetrahydropyranyl methacrylate providing the structural unit (I), 20 parts by mass of glycidyl methacrylate providing the structural unit (II), and methacrylic acid providing the structural unit (III) 20 parts by mass of adamantyl ester, 10 parts by mass of methacrylic acid which provides another structural unit, and 3 parts by mass of α-methylstyrene dimer, and after nitrogen substitution, start to stir slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-3). The Mw of the copolymer (A-3) was 8,500. Further, the solid content concentration of the polymer solution obtained here was 32.5% by mass.

[Synthesis Example 4]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were added. Next, 50 parts by mass of tetrahydropyranyl methacrylate providing the structural unit (I), 20 parts by mass of glycidyl methacrylate providing the structural unit (II), and methacrylic acid providing the structural unit (III) 20 parts by mass of stearyl ester, and 10 parts by mass of methacrylic acid and 3 parts by mass of α-methylstyrene dimer, which provide other structural units, were gradually stirred after nitrogen substitution. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-4). The Mw of the copolymer (A-4) was 7,500. Further, the solid content concentration of the polymer solution obtained here was 31.0% by mass.

[Synthesis Example 5]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were added. Next, 15 parts by mass of tetrahydropyranyl methacrylate providing the structural unit (I), 10 parts by mass of glycidyl methacrylate providing the structural unit (II), and methacrylic acid providing the structural unit (III) 60 parts by mass of the lauryl ester, and 5 parts by mass of methacrylic acid and 31 parts by mass of the α-methylstyrene dimer which provided other structural units were slowly stirred after nitrogen substitution. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-5). The Mw of the copolymer (A-5) was 8,000. Further, the solid content concentration of the polymer solution obtained here was 31.5% by mass.

[Synthesis Example 6]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were added. Next, 55 parts by mass of tetrahydropyranyl methacrylate providing the structural unit (I), 35 parts by mass of glycidyl methacrylate providing the structural unit (II), and methacrylic acid 10 providing other structural units are added. The mass part and 3 parts by mass of the α-methylstyrene dimer were slowly stirred after nitrogen substitution. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (a-1). The Mw of the copolymer (a-1) was 9,000. Further, the solid content concentration of the polymer solution obtained here was 32.1% by mass.

<Preparation of Radiation-Linear Compositions>

[Example 1]

In the solution containing the copolymer (A-1) as the [A] polymer (corresponding to 100 parts by mass (solid content) of the copolymer (A-1)), 3 parts by mass of the compound (B-1) is mixed as [B] a radioactive acid generator and 15 parts by mass of the compound (C-1) as a [C] compound, a compound (D-1) 0.01 parts by mass as a basic compound, and (E-1) an anthrone-based surfactant (Toray Dow Corning, SH 8400 FLUID) 0.2 parts by mass as a surfactant, (F-1) γ-glycidoxypropyltrimethoxydecane 3.0 parts by mass as an adhesion aid, using a film having a pore size of 0.2 μm Filtration was carried out by a membrane filter, thereby preparing a radiation sensitive composition (S-1).

[Example 2 to Example 10 and Comparative Example 1]

The radiation sensitive composition (S-2) was prepared in the same manner as in Example 1 except that the types and the amounts of the respective components were as described in Table 1. The radiation sensitive linear composition (S-10) and the radiation sensitive linear composition (CS-1) were used as Examples 2 to 10 and Comparative Example 1, respectively.

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

<[B] Radiation-sensitive linear acid generator>

(B-1): 4,7-di-n-butoxy-1-naphthyltetrahydrothiophene trifluoromethanesulfonate

(B-2): N-hydroxynaphthoquinone imine-triflate

(B-3): (5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile (manufactured by Ciba Specialty Chemicals, IRGACURE PAG 103)

<[C] compound>

(C-1) a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate

(C-2) Ethylene oxide modified dipentaerythritol hexaacrylate

(C-3) Trimethylolpropane triacrylate

(C-4) succinic acid modified pentaerythritol triacrylate

(C-5) ε-caprolactone modified dipentaerythritol hexaacrylate

(C-6) hexamethylene diacrylate

<alkaline compound>

(D-1)4-dimethylaminopyridine

<Surfactant>

(E-1) Anthrone-based surfactant (Dolly Dow Corning, SH 8400 FLUID)

<Close Agent>

(F-1) γ-glycidoxypropyltrimethoxydecane

<Evaluation>

Using the radiation sensitive compositions of Examples 1 to 10 and Comparative Example 1, various characteristics as the respective radiation-sensitive components, and the coating film or the interlayer insulating film thereof were evaluated as follows. The results are shown in Table 1.

[sensitivity (J/m ² )]

On a 550 mm × 650 mm chromium film-forming glass, hexamethyldisilazane (HMDS) was applied and heated at 60 ° C for 1 minute (HMDS treatment). On each of the HMDS-treated chromium film-forming glass, each of the radiation-sensitive compositions prepared in the above manner was applied using a slit die coater "TR632105-CL", and the ultimate pressure was set to 100 Pa. After removing the solvent under vacuum, it was further baked at 90 ° C for 2 minutes to form a coating film having a film thickness of 3.0 μm. Next, using a MPA-600FA exposure machine of Canon Inc., a mask having a line width and a space (10:1) pattern of 60 μm was used to irradiate the coating film with radiation as a variable, and then 0.4% by mass. The methyl ammonium hydroxide aqueous solution was developed by a dip method at 25 °C. The development time was set to 80 seconds. Next, it was washed with ultrapure water for 1 minute, and then dried to form a pattern on the chrome-crystallized glass substrate after the HMDS treatment. At this time, the amount of exposure necessary to completely dissolve the spatial pattern of 6 μm was investigated. When the value is 300 J/m ² or less, it can be said that the sensitivity is good.

[Surface hardness]

A coating film was formed on the glass substrate in the same manner as the evaluation of the above sensitivity. Instead of performing exposure, the glass substrate was heated in a clean oven at 220 ° C for 1 hour to obtain a cured film. The pencil hardness (surface hardness) of the cured film was measured by a 8.4.1 pencil scratch test of JIS K-5400-1990. When the value is 3H or more than 3H, the surface hardness of the cured film such as the interlayer insulating film is good, and the composition used for forming the cured film can be said to have sufficient hardenability.

[Solvent resistance (%)]

A coating film was formed on the glass substrate in the same manner as the evaluation of the above sensitivity. Instead of performing exposure, the glass substrate was heated in a clean oven at 220 ° C for 1 hour to obtain a cured film. The film thickness (T1) of the obtained cured film was measured by a laser microscope (VK-8510, manufactured by Keyence) on the substrate having the cured film. Next, the glass substrate on which the cured film was formed was immersed in a dimethyl sulfoxide whose temperature was controlled to 70 ° C for 20 minutes, and then the film thickness (t1) of the cured film was measured, and the following formula was used to determine The film thickness change rate (%) due to immersion was determined as solvent resistance (%).

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

When the absolute value of this value is less than 5%, it is judged that solvent resistance is excellent.

[Voltage retention rate]

An SiO ₂ film for preventing elution of sodium ions is formed on the surface, and after each of the positive-type radiation-sensitive linear compositions is spin-coated on a soda glass substrate obtained by vapor-depositing an ITO (indium-tin oxide alloy) electrode into a predetermined shape, The film was pre-baked in a clean oven at 90 ° C for 10 minutes to form a coating film having a film thickness of 2.0 μm. Next, the coating film was exposed at an exposure amount of 500 J/m ² without interposing the photomask. Then, it was baked at 230 ° C for 30 minutes to cure the coating film. Next, the substrate on which the pixel was formed and the substrate on which only the ITO electrode was vapor-deposited into a predetermined shape were bonded by a sealant mixed with glass beads of 0.8 mm, and then injected into Merck. The manufactured liquid crystal MLC6608 was fabricated into a liquid crystal cell. Further, the liquid crystal cell was placed in a constant temperature layer at 60 ° C, and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage retention ratio measurement system (VHR-1A type, Toyo Technica Co., Ltd.). The applied voltage at this time was a square wave of 5.5 V, and the measurement frequency was 60 Hz. The voltage holding ratio (%) is a value obtained by the following formula.

Voltage holding ratio (%) = (liquid crystal cell potential difference after 16.7 ms / voltage applied at 0 msec) × 100

When the voltage holding ratio of the liquid crystal cell is 90% or less, it means that the liquid crystal cell cannot maintain the applied voltage at a predetermined level for 16.7 milliseconds, and the liquid crystal cannot be sufficiently aligned, resulting in a high risk of "burning" such as afterimage. .

[heat resistance]

A coating film was formed on the glass substrate in the same manner as the evaluation of the above sensitivity. Instead of performing exposure, the glass substrate was heated in a clean oven at 220 ° C for 1 hour to obtain a cured film. The 5% thermogravimetric reduction temperature of the obtained cured film was measured. Measurement The temperature was increased from room temperature to 500 ° C at 10 ° C / min using a thermogravimetric analyzer (TGA) at a fixed time, and the temperature was reduced by 5%. The higher the temperature at which the mass is reduced by 5%, the better the heat resistance can be judged.

As is clear from the results of Table 1, it is understood that Examples 1 to 10 using the radiation sensitive composition have better sensitivity than the composition of Comparative Example 1, and can form surface hardness, solvent resistance, and A cured film excellent in heat resistance. Further, the voltage holding ratio of the cured film formed of the radiation sensitive compositions of Examples 1 to 10 was also sufficiently high.

[Industrial availability]

The radiation sensitive composition of the present invention can easily form an interlayer insulating film for a display element having a fine and delicate pattern because of its excellent sensitivity. In addition, the radiation sensitive composition can form an interlayer insulating film for a display element which is excellent in surface hardness, solvent resistance, heat resistance, and voltage holding ratio. Therefore, the radiation sensitive 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 FL display element.

Claims (8)

A radiation sensitive linear composition comprising: [A] a structural unit (I) having an acid dissociable group, a structural unit (II) containing a polymerizable group, and a structural unit represented by the following formula (1) a polymer of (III); [B] a radioactive acid generator; and [C] a compound containing one or more (meth) acrylonitrile groups and having a molecular weight of 1,000 or less, and the content of the above [C] compound is solid. The component is converted into 1% by mass or more and 50% by mass or less: In the formula (1), R ¹ is a hydrogen atom or a methyl group; and R ² is an alkyl group, an alkenyl group, an alkynyl group or a decyloxyalkyl group having a carbon number of 6 to 30 or a crosslinked cyclic hydrocarbon group having a carbon number of 4 to 30. Wherein a part of the hydrogen atom possessed by the above alkyl group, alkenyl group, alkynyl group, decyloxyalkyl group and crosslinked cyclic hydrocarbon group may be substituted with a hydroxyl group or a carboxyl group. The radiation sensitive composition according to claim 1, wherein the acid dissociable group in the structural unit (I) is represented by the following formula (2): [Chemical 2] In the formula (2), R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group or an aryl group; wherein a part of a hydrogen atom of the alkyl group, the alicyclic hydrocarbon group or the aryl group or All may be substituted; further, there is no case where both R ³ and R ⁴ are a hydrogen atom; and R ⁵ is an alkyl group, an alicyclic hydrocarbon group, an aralkyl group, an aryl group or a group represented by -M(R ⁶ ) ₃ group; M is Si, Ge or of Sn; R ⁶ is alkyl; wherein the alkyl part, an alicyclic hydrocarbon group, aryl group and aralkyl group of R ⁵ and R ⁶ are hydrogen atoms or having all which may be substituted; R ³ and R ⁵ may be bonded to each other to form a cyclic structure together with an ether oxygen atom and R ⁵ carbon atoms are bonded to R ³ are bonded. The radiation sensitive composition according to claim 1, wherein the polymerizable group in the structural unit (II) is an epoxy group. The radiation-sensitive composition according to the first aspect of the invention, wherein the content of the structural unit (III) in the [A] polymer is 3% by mass or more and 50% by mass or less. The radiation-sensitive composition according to claim 1, wherein the compound [C] is a skeleton having a diol structure derived from carbon number 2 to 12, a skeleton derived from trimethylolpropane, and derived from A skeleton of pentaerythritol or a compound derived from the skeleton of dipentaerythritol. The radiation sensitive composition according to any one of the items 1 to 5, which is used for forming an interlayer insulating film for a display element. An interlayer insulating film for a display element, which is characterized in that it is formed of a radiation sensitive linear composition as described in claim 6 of the patent application. A method of forming an interlayer insulating film for a display element, comprising: (1) a step of forming a coating film on a substrate using the radiation-sensitive linear composition according to claim 6 of the patent application; (2) a step of irradiating at least a part of the coating film with radiation; (3) a step of developing the coating film irradiated with radiation; and (4) a step of heating the coating film which has been developed.