JP6136787B2 - Radiation sensitive resin composition for forming insulating film of display element, method for preparing the composition, insulating film for display element, method for forming the insulating film, and display element - Google Patents

Description

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

  A display element typified by a thin film transistor type liquid crystal display element or an organic electroluminescence element generally has an insulating film such as an interlayer insulating film or a planarizing film. Such an insulating film is generally formed using a radiation sensitive resin composition. As such a radiation-sensitive resin composition, a positive-type radiation-sensitive resin composition using an acid generator such as naphthoquinonediazide was used from the viewpoint of patterning performance (see JP-A-2001-354822). In recent years, various radiation-sensitive resin compositions have been proposed.

  As an example, Japanese Patent Application Laid-Open No. 2004-4669 proposes a positive chemical amplification material for the purpose of forming an insulating film for a display element with higher sensitivity than the positive radiation sensitive resin composition. Yes. This positive chemical amplification material contains a cross-linking agent, an acid generator, and an acid dissociable resin. The acid dissociable resin has a protecting group that can be cleaved by the action of an acid and is insoluble or hardly soluble in an aqueous alkali solution, but is soluble in an aqueous alkali solution by cleaving the protecting group by the action of an acid. It becomes. JP 2004-264623 A and JP 2008-304902 A disclose a positive radiation sensitive resin composition containing an acid generator and a resin having an acetal structure and / or a ketal structure and an epoxy group. Has been proposed.

  However, when using the above-described radiation-sensitive resin composition, particularly a positive chemical amplification material, the acid generated during exposure is neutralized by the basic substance in the atmosphere during the holding time until the heating step. There is a risk of deactivation or diffusion to unexposed areas. When such acid deactivation or diffusion occurs, there arises a problem that the adhesion between the substrate and the insulating film is lowered (see JP-A-6-266100).

  Placement after exposure frequently occurs in the manufacturing process when a large-sized glass substrate is used. Therefore, there is a demand for a radiation-sensitive resin composition that can reduce the influence due to leaving after exposure and can form a stable pattern.

  In order to reduce the influence by the leaving after exposure, it is conceivable to reduce the diffusion of the acid to the unexposed area. In order to suppress acid diffusion, it is effective to add a basic substance. However, when an amine compound is used as the basic substance, the curing reaction of the resin in the composition is promoted, so there is a concern that the storage stability of the radiation-sensitive resin composition is lowered.

  As described above, it is difficult to satisfy both the suppression of the decrease in the adhesiveness of the insulating film due to the diffusion of the acid and the like and the suppression of the decrease in the storage stability of the radiation-sensitive resin composition. On the other hand, since radiation sensitive resin compositions require general characteristics such as radiation sensitivity, it is necessary to consider so as to satisfy the above general characteristics even when improving the adhesion and storage stability of the insulating film. There is.

JP 2001-354822 A JP 2004-4669 A JP 2004-264623 A JP 2008-304902 A See JP-A-6-266100

  The present invention has been made based on the above circumstances, and is excellent in general characteristics and storage stability required for a radiation-sensitive resin composition such as radiation sensitivity, and poor adhesion of an insulating film. It aims at providing the radiation sensitive resin composition for insulating film formation of the display element which enables reduction. The present invention further includes a method for preparing the radiation-sensitive resin composition, an insulating film for a display element formed from the radiation-sensitive resin composition, a method for forming the insulating film, and a display element including the insulating film. The purpose is to provide.

  The invention made in order to solve the above problems includes a first structural unit containing a carboxyl group (hereinafter also referred to as “structural unit (I)”) and a second structural unit in which the carboxyl group is protected by a protecting group (hereinafter referred to as “structure”). A first polymer (hereinafter also referred to as “[A1] polymer”) having at least the second structural unit of the unit (II) ”and a third structural unit containing a crosslinkable group; A second polymer (hereinafter also referred to as “[A2] polymer”) having at least the first structural unit of one structural unit and the second structural unit and the third structural unit (hereinafter referred to as “[A2] polymer”). The polymer and the [A2] polymer are collectively referred to as “[A] polymer component”), and a radiation-sensitive acid generator, and the first structural unit and the second structural unit in the first polymer. Of the second structural unit in the total number of moles of Radiation-sensitive resin for forming an insulating film of a display element, wherein the difference between the first protection ratio, which is a percentage of the second polymer, and the second protection ratio, which is the mole percentage of the second polymer, is 5 mol% to 70 mol% It is a composition (hereinafter also referred to as “radiation sensitive resin composition”).

  Another invention made in order to solve the above-mentioned problem is that at least the second structural unit of the first structural unit containing a carboxyl group and the second structural unit in which the carboxyl group is protected by a protective group, and a crosslinkable group And a second polymer having at least the first structural unit of the first structural unit and the second structural unit, and the third structural unit. A first protection rate that is a molar ratio of the second structural unit in a total number of moles of the first structural unit and the second structural unit in the first polymer, and a second protective layer. It is a preparation method of the radiation sensitive resin composition for insulating film formation of the display element whose difference with the said 2nd protection rate which is the said molar ratio in a coalescence is 5 mol% or more and 70 mol% or less.

  Still another invention made in order to solve the above problems is a step of forming a coating film on a substrate, a step of irradiating at least a part of the coating film, and a step of developing a coating film irradiated with radiation. And a method for forming an insulating film, comprising the step of heating the developed coating film, wherein the radiation sensitive resin composition for forming an insulating film is used for forming the coating film. .

  The present invention further includes an insulating film of a display element formed from the radiation-sensitive resin composition, and a display element including the insulating film.

  The present invention provides a radiation-sensitive resin composition for forming an insulating film of a display element that sufficiently satisfies general characteristics such as radiation sensitivity, is excellent in storage stability, and can reduce poor adhesion of an insulating film. Can be provided. The present invention further provides a method for preparing the radiation-sensitive resin composition, an insulating film for a display element formed from the radiation-sensitive resin composition, a method for forming the same, and a display element including the insulating film. it can. Therefore, the radiation-sensitive resin composition, the method for preparing the radiation-sensitive resin composition, the insulating film, the method for forming the insulating film, and the display element are preferably used for manufacturing processes of liquid crystal display devices and the like. Can do.

[Radiation sensitive resin composition]
The radiation sensitive resin composition of this invention is for forming the insulating film of a display element. The radiation-sensitive resin composition contains [A] a polymer component and [B] a radiation-sensitive acid generator. Moreover, the said radiation sensitive resin composition may contain [C] antioxidant as a suitable component. Furthermore, the said radiation sensitive resin composition may contain another arbitrary component in the range which does not impair the effect of this invention. Hereinafter, each component will be described in detail.

[[A] polymer component]
[A] A polymer component consists of a [A1] polymer and a [A2] polymer. [A1] polymer and [A2] polymer have different protection rates. Here, the protection rate is the molar ratio (mol%) of the structural unit (II) in the total number of moles of the structural unit (I) and the structural unit (II) in the [A1] polymer or [A2] polymer. Say. That is, the protection rate is a molar ratio of the structural unit (I) in which the carboxyl group in the structural unit (I) and the structural unit (II) is protected. This protection rate is the structural unit in the total number of moles of the monomer that gives the structural unit (I) and the monomer that gives the structural unit (II) to the [A1] polymer or [A2] polymer ( It can also be defined as the molar proportion of monomer giving II). In the present embodiment, the higher protection rate among the [A1] polymer and the [A2] polymer is the [A1] polymer, and the lower protection rate is the [A2] polymer.

  The [A1] polymer and the [A2] polymer differ in the degree of protection and the degree of protection of the carboxyl group against water or the like due to the different protection rates, so the storage stability and the adhesion of the insulating film are different. Therefore, the radiation sensitive resin composition can achieve both storage stability and adhesiveness of the insulating film by setting the difference in the protection ratio between the [A1] polymer and the [A2] polymer within a predetermined range. It becomes possible.

  The lower limit of the difference in protection ratio between the [A1] polymer and the [A2] polymer is 5% by mass, preferably 10% by mass, and more preferably 15% by mass. The upper limit of the difference in the protection ratio is 70% by mass, preferably 65% by mass, and more preferably 60% by mass. When the difference in the protection ratio is less than the lower limit, the difference in properties between the [A1] polymer and the [A2] polymer is small, and the protection ratio of the [A1] polymer and the protection ratio of the [A2] polymer are There is a possibility that the effect of coexistence of storage stability and adhesiveness of the insulating film by differentiating may not be obtained sufficiently and does not satisfy general characteristics required for radiation sensitive resin compositions such as radiation sensitivity. There is a fear. On the other hand, if the difference in the protection ratio exceeds the above upper limit, the difference in properties between the [A1] polymer and the [A2] polymer becomes large, and the properties of one polymer appear significantly. There is a possibility that the effect of coexistence of adhesion and storage stability may not be sufficiently obtained, and there is a possibility that general characteristics required for the radiation sensitive resin composition such as radiation sensitivity may not be satisfied.

  The protection rate of the [A1] polymer and the [A2] polymer is a property required for the radiation-sensitive resin composition, for example, adhesion of the formed insulating film, storage stability, light resistance, radiation sensitivity, etc. It may be determined in accordance with the characteristics that are considered important and the balance of these characteristics. [A1] The protection rate of the polymer is usually 10% by mass or more and 100% by mass or less. On the other hand, the protection rate of the [A2] polymer is usually 0% by mass or more and 90% by mass or less.

<[A1] Polymer>
The [A1] polymer has a higher protection rate than the [A2] polymer. This [A1] polymer has at least structural unit (II) among structural unit (I) and structural unit (II). That is, in the [A1] polymer, the structural unit (II) is an essential structural unit and the structural unit (I) is an arbitrary structural unit. [A1] The polymer preferably has a structural unit (III) containing a crosslinkable group, and may contain other structural units as long as the effects of the present invention are not impaired.

<[A2] Polymer>
The [A2] polymer has a lower protection rate than the [A1] polymer. This [A2] polymer has at least the structural unit (I) of the structural unit (I) and the structural unit (II). That is, in the [A2] polymer, contrary to the [A1] polymer, the structural unit (I) is an essential structural unit and the structural unit (II) is an arbitrary structural unit. [A2] The polymer preferably has a structural unit (III) containing a crosslinkable group, and may contain other structural units as long as the effects of the present invention are not impaired.

(Structural unit (I))
The structural unit (I) contains a carboxyl group. Since the [A1] polymer and the [A2] polymer have the structural unit (I) containing a carboxyl group which is an alkali-soluble group, the solubility in the developer can be improved and the adhesion of the insulating film can be improved. Examples of the structural unit (I) include a group derived from an unsaturated carboxylic acid.

Examples of the unsaturated carboxylic acid include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, and unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid;
Mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (meth) acryloyloxyethyl] phthalate, mono 2- (methacryloyloxy) ethyl hexahydrophthalate mono [ (Meth) acryloyloxyalkyl] ester;
mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate;
5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2. 1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, Unsaturation having a carboxyl group such as 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride Examples thereof include polycyclic compounds.

  As the structural unit (I), structural units represented by the following formulas (I-1) to (I-3) (hereinafter also referred to as “structural units (I-1) to (I-3)”), respectively. preferable.

In the above formulas (I-1) to (I-3), R ¹⁴ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
In the above formulas (I-1) and (I-2), R ¹⁵ is a divalent chain hydrocarbon group having 1 to 6 carbon atoms, a divalent alicyclic hydrocarbon group having 4 to 12 carbon atoms, or It is a C6-C12 bivalent aromatic hydrocarbon group.
In the formula ^{(I-1), R 16} is a divalent chain hydrocarbon group having 1 to 6 carbon atoms, a divalent alicyclic hydrocarbon group or a C6-12 C4-12 It is a divalent aromatic hydrocarbon group.

R ¹⁴ is preferably a hydrogen atom or a methyl group, and more preferably a methyl group, from the viewpoint of copolymerizability of the monomer that gives the structural units (I-1) to (I-3).

Examples of the divalent chain hydrocarbon group having 1 to 6 carbon atoms represented by R ¹⁵ and R ¹⁶ include a methanediyl group, 1,2-ethanediyl group, 1,1-ethanediyl group, 1,3- Propanediyl group, 1,2-propanediyl group, 1,1-propanediyl group, 2,2-propanediyl group, 1,4-propanediyl group, 1,5-pentanediyl group, 1,6-hexanediyl group 1-methyl-1,3-propanediyl group, 2-methyl-1,3-propanediyl group, 2-methyl-1,2-propanediyl group, 1-methyl-1,4-butanediyl group, 2- Saturated chain hydrocarbon groups such as methyl-1,4-butanediyl group; Unsaturated chain hydrocarbon groups such as 1,2-ethenediyl group, 1,3-propenediyl group, 1,2-propenediyl group, etc. .

Examples of the divalent alicyclic hydrocarbon group having 4 to 12 carbon atoms represented by R ¹⁵ and R ¹⁶ include cyclobutanediyl groups such as 1,3-cyclobutanediyl group; 1,3-cyclopentanediyl; Cyclopentanediyl groups such as groups; Cyclohexanediyl groups such as 1,4-cyclohexanediyl groups and 1,2-cyclohexanediyl groups; Monocyclic hydrocarbons such as cyclooctanediyl groups such as 1,5-cyclooctanediyl groups Groups: polycyclic hydrocarbons such as norbornanediyl groups such as 1,4-norbornanediyl groups and 2,5-norbornanediyl groups, adamantanediyl groups such as 1,3-adamantanediyl groups and 2,4-adamantanediyl groups Group and the like.

Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms represented by R ¹⁵ and R ^16, for example, a phenylene group, such as an arylene group such as a tolylene group.

  Examples of the structural unit (I-1) include structural units represented by the following formulas (I-1-1) to (I-1-3). As the structural unit (I-2), Examples thereof include structural units represented by the following formulas (I-2-1) and (I-2-2).

In the above formulas (I-1-1) to (I-1-3), (I-2-1) and (I-2-2), R ¹⁴ represents the above formulas (I-1) and (I- It is synonymous with 2).

  As the structural unit (I), a structural unit represented by the above formula (I-3) is preferable, and a structural unit derived from methacrylic acid or acrylic acid is more preferable.

  [A1] The content ratio of the structural unit (I) in the polymer is preferably 15 mol% or more and 85 mol% or less, and 25 mol% or more and 75 mol% with respect to all the structural units constituting the [A1] polymer. The following is more preferable, and 25 mol% or more and 65 mol% or less is more preferable. [A2] The content of the structural unit (I) in the polymer is preferably 1 mol% or more and 50 mol% or less, and preferably 10 mol% or more and 40 mol% with respect to all the structural units constituting the [A2] polymer. The following are more preferable, and 15 mol% or more and 30 mol% or less are more preferable. By making the content rate of structural unit (I) into the said range, the radiation sensitivity of the said radiation sensitive resin composition can fully be ensured, and the adhesiveness of an insulating film improves.

(Structural unit (II))
The structural unit (II) has a structure in which the carboxyl group of the structural unit (I) is protected by a protective group. This protecting group constitutes an acid dissociable group in the structural unit (II). This acid-dissociable group is a group that can be cleaved by the action of an acid and is insoluble or hardly soluble in an aqueous alkali solution, but is soluble in an aqueous alkali solution by cleaving the protecting group by the action of an acid. Is a group.

  The protective group is not particularly limited as long as it can protect a carboxyl group, and examples thereof include a trialkylsilyl group, a 1-alkoxyalkyl group, and a cyclic 1-alkoxyalkyl group.

  Examples of the trialkylsilyl group include a trimethylsilyl group and a dimethylbutylsilyl group.

  The 1-alkoxyalkyl group is preferably a monovalent group represented by the following formula (1 ′).

In the above formula (1 ′), R ¹ and R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or at least a part of the hydrogen atoms of the hydrocarbon group is a hydroxyl group, a halogen atom A group substituted by an atom or a cyano group. However, there is no case where R ¹ and R ² are both hydrogen atoms. R ³ represents a hydrocarbon group having 1 to 30 carbon atoms, a group containing an oxygen atom between carbon-carbon or a bond side terminal of the carbon hydrogen group, or at least a part of hydrogen atoms of these groups is a hydroxyl group, a halogen atom A group substituted by an atom or a cyano group.

As a C1-C30 hydrocarbon group represented by said R < ¹ > -R < ³ >, for example,
Monovalent chain hydrocarbon groups such as methyl group, ethyl group, n-propyl group, n-butyl group, i-butyl group, t-butyl group and n-pentyl group;
Monovalent alicyclic hydrocarbon groups such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a dicyclopentyl group, a tricyclodecyl group, a tetracyclododecyl group, an adamantyl group;
A monovalent hydrocarbon group partially having the alicyclic structure of this alicyclic hydrocarbon group;
Monovalent aromatic hydrocarbon groups such as phenyl group, naphthyl group, anthryl group, biphenyl group;
Examples thereof include a monovalent hydrocarbon group having an aromatic ring of the aromatic hydrocarbon group in part.

Examples of the group containing an oxygen atom at the carbon-carbon or bond-end side end of the hydrocarbon group represented by R ³ include carbons of hydrocarbon groups exemplified as the hydrocarbon group having 1 to 30 carbon atoms. -The monovalent group etc. which have an ether bond between carbon bonds or the terminal by the side of a bond are mentioned.

Examples of the group in which the hydrocarbon group of R ^{1 to} R ³ is substituted with a hydroxyl group include a hydroxymethyl group, a hydroxyethyl group, a hydroxybutyl group, a dihydroxyethyl group, a dihydroxypropyl group, and the like.

As a halogen atom which substitutes said R < ¹ > -R < ³ >, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.

As the ^R 1 to R ^3, a phenyl group is preferable. That is, the protecting group represented by the above formula (1 ′) is preferably a triphenylmethyl group.

  The cyclic 1-alkoxyalkyl group is preferably a monovalent group represented by the following formula (2 ′).

In said formula (2 '), R < ⁴ > -R < ¹⁰ > is a hydrogen atom or a C1-C12 hydrocarbon group each independently. n is 1 or 2. When n is 2, the plurality of R ⁷ and R ⁸ may be the same or different.

Examples of the hydrocarbon group having 1 to 12 carbon atoms represented by R ^{4 to} R ¹⁰ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. Chain hydrocarbon groups such as cycloaliphatic hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group; aromatic hydrocarbon groups such as phenyl group, methylphenyl group, ethylphenyl group and benzyl group Is mentioned.

R ^{4 to} R ¹⁰ are preferably a hydrogen atom, and n is preferably 2. That is, the protecting group represented by the above formula (2 ′) is preferably a tetrahydrofuranyl group or a tetrahydropyranyl group, and more preferably a tetrahydropyranyl group.

  Examples of the structure protected by the protective group for the carboxyl group include a structure in which a hydrogen atom in the carboxyl group is substituted by the protective group, and a structure represented by the following formula (1) or the following formula (2) is preferable. .

In the formula ^(1), R 1 to R ³ have the same meanings as ^R 1 to R ³ in the formula (1 ').
In the above formula ^(2), R 4 ^{to R 10} and n have the same meanings as ^R 4 ^{to R 10} and n of formula (2 ').

  [A1] When the polymer has a plurality of structural units (II), the protective groups of these structural units (II) may be the same or different, but are preferably the same. Similarly, when the [A2] polymer has a plurality of types of structural units (II), the protective groups of these structural units (II) may be the same or different, but are preferably the same. .

  When both the [A1] polymer and the [A2] polymer have the structural unit (II), the protective group of the structural unit (II) of the [A1] polymer and the structural unit (II of the polymer [II] ) Protecting groups may be the same or different, but are preferably the same.

  [A1] The content ratio of the structural unit (II) in the polymer is preferably 0.1 mol% or more and 60 mol% or less, and preferably 1 mol% or more, based on all structural units constituting the [A1] polymer. 50 mol% or less is more preferable, and 3 mol% or more and 40 mol% or less are still more preferable. [A2] The content ratio of the structural unit (II) in the polymer is preferably 0.1 mol% or more and 60 mol% or less, and preferably 1 mol% or more and 50 mol% or less with respect to all the structural units constituting the [A2] polymer. The mol% or less is more preferable, and 3 mol% or more and 40 mol% or less is more preferable. By making the content rate of structural unit (II) into the said range, the radiation sensitivity and the storage stability of the said radiation sensitive resin composition can be ensured more fully.

(Structural unit (III))
The structural unit (III) includes a crosslinking group. The insulating film formed from the radiation-sensitive resin composition has a structural unit (III) in which at least one of the [A1] polymer and the [A2] polymer includes a crosslinkable group, [A] The strength can be increased by crosslinking between polymers constituting the polymer component, or by crosslinking [A1] polymer or [A2] polymer with [C] antioxidant, which will be described later.

Examples of the crosslinkable group include a group containing a polymerizable carbon-carbon double bond, a group containing a polymerizable carbon-carbon triple bond, an oxiranyl group (1,2-epoxy structure), an oxetanyl group (1,3- Epoxy structure), alkoxymethyl group, formyl group, acetyl group, dialkylaminomethyl group, dimethylolaminomethyl group, 2,3-epoxytricyclo [5.2.1.0 ^2.6 ] decane group, 3,4 -An epoxy tricyclo [5.2.1.0 ^2.6 ] decane group etc. are mentioned.

  Examples of the structural unit (III) include a structural unit represented by the following formula.

In the above formula, R ¹⁷ is a hydrogen atom or a methyl group.

As the structural unit (III), for example, a monomer having an epoxidized structure of an alicyclic unsaturated hydrocarbon and an ethylenically unsaturated bond (hereinafter also referred to as “monomer (iii)”) Examples of the structural unit are derived. Examples of the structural unit derived from the monomer (iii) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, “Celoxide 2000” manufactured by Daicel Corporation), 3,4-epoxycyclohexyl, and the like. Methyl (meth) acrylate (eg, “Cyclomer A400” from Daicel), 3,4-epoxycyclohexylmethyl (meth) acrylate (eg, “Cyclomer M100” from Daicel Chemical Industries), glycidyl methacrylate, 2, 3-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate, represented by the following formula (3) Structural units.

In the above formula (3), R ¹¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a group in which at least a part of hydrogen atoms of the alkyl group is substituted with a hydroxy group. R ¹² is a group represented by the following formula (4-1) or the following formula (4-2). X ¹ is a single bond, a methylene group or an alkylene group having 2 to 12 carbon atoms. Y ¹ is a single bond, an oxygen atom, a sulfur atom or an imino group.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Can be mentioned. Examples of the alkyl group in which at least a part of hydrogen atoms are substituted with hydroxy include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, and a 3-hydroxypropyl group. 1-hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.

R ¹¹ is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

Examples of the alkylene group having 2 to 12 carbon atoms represented by X ^1, for example, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, and among them, the X ¹ As these, an ethylene group and a methylene group are preferable.

  Examples of the monomer that gives the structural unit represented by the above formula (3) include monomers represented by the following formulas (3-1) to (3-30). The monomers represented by the following formulas (3-1) to (3-30) may be used alone or in combination of two or more.

As the structural unit (III), a structural unit derived from 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate or glycidyl methacrylate is preferable. .

  The content ratio of the structural unit (III) in the [A1] polymer or [A2] polymer is 1 mol% or more and 75 mol with respect to all the structural units constituting the [A1] polymer or [A2] polymer. % Or less, more preferably 5 mol% or more and 60 mol% or less, and further preferably 15 mol% or more and 50 mol% or less. By making the content rate of structural unit (III) into the said range, the intensity | strength of an insulating film can be raised effectively.

(Other structural units)
The [A1] polymer and the [A2] polymer may have other structural units other than the structural units (I) to (III) as long as the effects of the present invention are not impaired.

  Examples of other structural units include structural units derived from unsaturated compounds (hereinafter also referred to as “structural units (IV)”). The [A1] polymer and the [A2] polymer may contain structural units other than the structural unit (IV) as other structural units.

[Structural unit (IV)]
The structural unit (IV) is a structural unit derived from an unsaturated compound. Examples of the unsaturated compound include unsaturated carboxylic acid anhydride, (meth) acrylic acid ester having a hydroxyl group, (meth) acrylic acid chain alkyl ester, (meth) acrylic acid alicyclic ester, (meth) acrylic. Examples include acid aromatic esters, unsaturated aromatic compounds, N-substituted maleimides, conjugated dienes, and compounds having a tetrahydrofuran skeleton.

Examples of unsaturated carboxylic acid anhydrides include:
Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; anhydrides of unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid;
5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2. 1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, Unsaturation having a carboxyl group such as 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride And anhydrides of polycyclic compounds.

  Among these, unsaturated dicarboxylic acid anhydrides are preferable, and maleic anhydride is more preferable from the viewpoint of copolymerization reactivity, solubility in an aqueous alkali solution, and availability.

  Examples of the (meth) acrylic acid ester having a hydroxyl group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxyhexyl acrylate, and methacrylic acid. Examples include 2-hydroxyethyl acid, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, and 6-hydroxyhexyl methacrylate.

  Examples of the (meth) acrylic acid chain alkyl ester include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, N-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, acrylic acid Examples include isodecyl, n-lauryl acrylate, tridecyl acrylate, and n-stearyl acrylate.

Examples of (meth) acrylic acid alicyclic esters include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, and tricyclomethacrylate [5. .2.1.0 ^2,6 ] decan-8-yloxyethyl, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane- Examples include 8-yl, tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxyethyl acrylate, and isobornyl acrylate.

  Examples of the (meth) acrylic acid aromatic ester include phenyl methacrylate, benzyl methacrylate, phenyl acrylate, and benzyl acrylate.

  Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and the like.

  Examples of the N-substituted maleimide include N-phenylmaleimide, N-cyclohexylmaleimide, N-tolylmaleimide, N-naphthylmaleimide, N-ethylmaleimide, N-hexylmaleimide, N-benzylmaleimide and the like.

  Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

  Examples of the unsaturated compound having a tetrahydrofuran skeleton include 3-tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one, and the like. It is done.

  The content ratio of the other structural units in the [A1] polymer or [A2] polymer is 0 mol% or more and 80 mass% with respect to all structural units constituting the [A1] polymer or [A2] polymer. The following are preferable, 10 mol% or more and 70 mol% or less are more preferable, and 30 mol% or more and 60 mol% or less are more preferable. By setting the content ratio of the other structural units in the above range, effects according to the characteristics of the other structural units, for example, improvement in applicability of the radiation-sensitive resin composition, solubility of the coating film in an alkaline aqueous solution Effects, such as optimization of radiation resistance, excellent radiation sensitivity, and ensuring water repellency of the insulating film of the display element are more exhibited.

  In addition, in [A1] polymer and [A2] polymer, the sum total of the content rate of each structural unit does not exceed 100 mass%.

<[A1] Polymer and [A2] Polymer Synthesis Method>
Each of the [A1] polymer and the [A2] polymer can be produced, for example, by polymerizing a monomer giving a predetermined structural unit in a suitable solvent using a radical polymerization initiator. Specifically, a method of dropping a solution containing a monomer and a radical polymerization initiator into a reaction solvent or a solution containing a monomer to cause a polymerization reaction, a solution containing the monomer, and initiation of radical polymerization A solution containing an agent separately from a reaction solvent or a solution containing a monomer to cause a polymerization reaction, a plurality of types of solutions containing each monomer, and a radical polymerization initiator It is preferable to synthesize | combine by methods, such as the method of dripping into a solution containing a reaction solvent or a monomer separately, and carrying out a polymerization reaction separately.

  Examples of the solvent used in the polymerization reaction of the [A1] polymer and the [A2] polymer include the same solvents as those exemplified in the section <Preparation of radiation-sensitive resin composition> described later.

  As the radical polymerization initiator used in the polymerization reaction, those generally known as radical polymerization initiators can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis Azo compounds such as (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (methyl 2-methylpropionate); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) cyclohexane; hydrogen peroxide and the like.

  In the polymerization reaction of the [A1] polymer and the [A2] polymer, a molecular weight modifier may be used to adjust the molecular weight. Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and thioglycolic acid; Examples thereof include xanthogens such as dimethylxanthogen sulfide and diisopropylxanthogen disulfide; terpinolene and α-methylstyrene dimer.

The polystyrene-reduced weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) of the [A1] polymer and [A2] polymer is preferably 2.0 × 10 ³ or more and 1.0 × 10 ⁵ or less, preferably 5 0.0 × 10 ³ or more and 5.0 × 10 ⁴ or less is more preferable. By setting Mw of the [A1] polymer and the [A2] polymer in the above range, the radiation sensitivity and developability of the radiation sensitive resin composition can be enhanced.

The number average molecular weight (Mn) in terms of polystyrene by GPC of the [A1] polymer and [A2] polymer is preferably 2.0 × 10 ³ or more and 1.0 × 10 ⁵ or less, preferably 5.0 × 10 ³ or more and 5 0.0 × 10 ⁴ or less is more preferable. By setting the Mn of the [A1] polymer and the [A2] polymer in the above range, the curing reactivity at the time of curing the coating film of the radiation sensitive resin composition can be improved.

  The molecular weight distribution (Mw / Mn) of the [A1] polymer and the [A2] polymer is preferably 3.0 or less, and more preferably 2.6 or less. By making Mw / Mn of the [A1] polymer and the [A2] polymer in the above range, the developability of the obtained insulating film can be improved.

<[B] Radiation sensitive acid generator>
[B] The radiation-sensitive acid generator is a compound that generates an acid upon irradiation with radiation. As the radiation, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used. The said radiation sensitive resin composition can exhibit a radiation sensitive characteristic by having a [B] radiation sensitive acid generator, and can have favorable radiation sensitivity. The content of the [B] radiation sensitive acid generator in the radiation sensitive resin composition may be a compound form (hereinafter also referred to as “[B] radiation sensitive acid generator” as appropriate), as described later. It may be in the form of a photoacid generating group incorporated as part of the A1] polymer or [A2] polymer, or both forms.

  [B] Examples of the radiation-sensitive acid generator include oxime sulfonate compounds, onium salts, N-sulfonyloxyimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylic acid ester compounds. It is done.

[Oxime sulfonate compound]
As the oxime sulfonate compound, a compound containing an oxime sulfonate group represented by the following formula (5) is preferable.

In the formula (5), R ¹⁸ is an alkyl group, a monovalent alicyclic hydrocarbon group, an aryl group, or a group in which some or all of the hydrogen atoms of these groups are substituted with a substituent.

The alkyl group represented by R ¹⁸ is preferably a linear or branched alkyl group having 1 to 12 carbon atoms.

The monovalent alicyclic hydrocarbon group represented by R ¹⁸ is preferably an alicyclic hydrocarbon group having 4 to 12 carbon atoms.

The aryl group represented by R ¹⁸ is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group, a naphthyl group, a tolyl group, or a xylyl group.

  As said substituent, a C1-C5 alkyl group, an alkoxy group, an oxo group, a halogen atom etc. are mentioned, for example.

  Examples of the compound containing an oxime sulfonate group represented by the above formula (5) include oxime sulfonate compounds represented by the following formulas (5-1) to (5-3).

In the above formulas (5-1) to (5-3), R ¹⁸ has the same meaning as the above formula (5).
The formula (5-1) and formula ^{(5-2), R 19} represents an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms.
In formula (5-3), X ² represents an alkyl group, an alkoxy group or a halogen atom. i is an integer of 0-3. However, when i is 2 or 3, the plurality of X ² may be the same or different.

The alkyl group represented by X ² is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group represented by X ² is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom represented by X ² is preferably a chlorine atom or a fluorine atom.

  Examples of the oxime sulfonate compound represented by the above (5-3) include compounds represented by the following formulas (5-3-1) to (5-3-5).

  The compounds represented by the above formulas (5-3-1) to (5-3-5) are respectively (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5 -P-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, 2- (octylsulfonyloxyimino) -2- (4-methoxyphenyl) acetonitrile, obtained as a commercial product it can.

[Onium salt]
Examples of the onium salt include diphenyliodonium salt, triphenylsulfonium salt, alkylsulfonium salt, benzylsulfonium salt, dibenzylsulfonium salt, substituted benzylsulfonium salt, benzothiazonium salt, tetrahydrothiophenium salt, and the like.

  Examples of the diphenyliodonium salt include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, Diphenyliodonium butyltris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoro Arsenate, bis (4-tert-butylphenyl) iodonium triflate Romethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium-p-toluenesulfonate, bis (4-t-butylphenyl) iodonium camphorsulfonic acid, etc. Can be mentioned.

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

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

  Examples of the benzylsulfonium salt include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4- Methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4- Examples thereof include hydroxyphenylmethylsulfonium hexafluorophosphate.

  Examples of the dibenzylsulfonium salt include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, and dibenzyl-4-methoxy. Phenylsulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxy Examples include benzyl-4-hydroxyphenylsulfonium hexafluorophosphate.

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

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

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

[N-sulfonyloxyimide compound]
Examples of the N-sulfonyloxyimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoro). Methylphenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) ) Phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) Diphenylmaleimide, 4-methylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) ) Diphenylmaleimide, N- (phenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1]. ] Hept-5-ene-2,3-dicarboximide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro) Butanesulfonyloxy) bicyclo [2. .1] Hept-5-ene-2,3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (camphor Sulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4 -Methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) Xyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-fluoro Phenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5 , 6-oxy-2,3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxyimi N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2 2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3 -Dicarboximide, N- (trifluoromethylsulfonyloxy) naphthyl dicarboximide, N- (camphorsulfonyloxy) naphthyl dicarboximide, N- (4-methylphenylsulfonyloxy) naphthyl dicarboximide, N- (phenyl Sulfonyloxy) naphthyl dicarboximide, N- (2-trifluoromethylpheny Sulfonyloxy) naphthyl dicarboximide, N- (4-fluorophenylsulfonyloxy) naphthyl dicarboximide, N- (pentafluoroethylsulfonyloxy) naphthyl dicarboximide, N- (heptafluoropropylsulfonyloxy) naphthyl dicarboximide N- (nonafluorobutylsulfonyloxy) naphthyl dicarboximide, N- (ethylsulfonyloxy) naphthyl dicarboximide, N- (propylsulfonyloxy) naphthyl dicarboximide, N- (butylsulfonyloxy) naphthyl dicarboximide N- (pentylsulfonyloxy) naphthyl dicarboximide, N- (hexylsulfonyloxy) naphthyl dicarboximide, N- (heptylsulfonyloxy) naphth Examples include tildicarboximide, N- (octylsulfonyloxy) naphthyldicarboximide, N- (nonylsulfonyloxy) naphthyldicarboximide, and the like.

[Halogen-containing compounds]
Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds.

[Diazomethane compounds]
Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, and bis (2,4-xylylsulfonyl) diazomethane. Bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl (benzoyl) diazomethane Etc.

[Sulfone compound]
Examples of the sulfone compound include β-ketosulfone compounds, β-sulfonylsulfone compounds, diaryl disulfone compounds, and the like.

[Sulfonic acid ester compounds]
Examples of the sulfonic acid ester compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. As the sulfonic acid ester compound, a haloalkylsulfonic acid ester is preferable, and N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester is more preferable.

[Carboxylic ester compounds]
Examples of the carboxylic acid ester compound include carboxylic acid o-nitrobenzyl ester.

  [B] The radiation-sensitive acid generator is preferably an oxime sulfonate compound, an onium salt, or a sulfonate compound, and more preferably an oxime sulfonate compound. As said oxime sulfonate compound, the compound containing the oxime sulfonate group represented by said Formula (5) is preferable, and the compound represented by said Formula (5-3-1)-(5-3-5) is more preferable. .

  As the onium salt, tetrahydrothiophenium salt and benzylsulfonium salt are preferable, 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate Are more preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate is more preferable. As the sulfonic acid ester compound, a haloalkylsulfonic acid ester is preferable, and N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester is more preferable.

  The radiation sensitive resin composition can improve radiation sensitivity and solubility in a developer by using the compounds exemplified as [B] radiation sensitive acid generator.

  [B] The content of the radiation sensitive acid generator is preferably 0.1 parts by mass or more and 10 parts by mass or less, and preferably 1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the polymer component [A]. More preferred. [B] By setting the content of the radiation-sensitive acid generator within the above range, the radiation sensitivity of the radiation-sensitive resin composition can be optimized, and an insulating film having a high surface hardness can be formed while maintaining transparency.

<[C] Antioxidant>
[C] Antioxidant is a component that suppresses the breakage of the bond of polymer molecules by capturing radicals generated by exposure or heating, or by decomposing a peroxide generated by oxidation. The radiation-sensitive resin composition contains [C] antioxidant, thereby suppressing degradation of polymer molecules in the insulating film formed from the radiation-sensitive resin composition, light resistance, etc. Can be improved.

  [C] Examples of the antioxidant include compounds having a hindered phenol structure, compounds having a hindered amine structure, compounds having an alkyl phosphite structure, compounds having a thioether structure, and the like. Among these, as a [C] antioxidant, the compound which has a hindered phenol structure is preferable. As described above, when the [C] antioxidant has a hindered phenol structure, degradation of polymer molecules in the insulating film formed from the radiation-sensitive resin composition can be further suppressed.

  Examples of the compound having a hindered phenol structure include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene bis [3- (3,5-dithione). -Tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tris- (3,5-di-tert-butyl-4- Hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N′-hexane-1, 6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide) 3,3 ′, 3 ′, 5 ′, 5′-hexa-tert-butyl-a, a ′, a ′-(mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (Octylthiomethyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) Propionate, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6- Xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio)- 1,3 5-triazin-2-ylamine) phenol, and the like.

As a commercial item of the compound having the hindered phenol structure, for example,
"ADK STAB AO-20", "ADK STAB AO-30", "ADK STAB AO-40", "ADK STAB AO-50", "ADK STAB AO-60", "ADK STAB AO-70", "ADK STAB AO-80", " ADK STAB AO-330 "(above, ADEKA)," SUMILIZER GM "," SUMILIZER GS "," SUMILIZER MDP-S "," SUMILIZER BBM-S "," SUMILIZER WX-R "," SUMILIZER GA-80 "(above, Sumitomo GA-80) ;
"IRGANOX1010", "IRGANOX1035", "IRGANOX1076", "IRGANOX1098", "IRGANOX1135", "IRGANOX1330", "IRGANOX1726", "IRGANOX1425WL", "IRGANOX1520L", "IRGANOX245", "IRGANOX245", "IRGANOX245", "IRGANOX245", "IRGANOX245" “IRGAMOD295” (Ciba Japan)
“Yoshinox BHT”, “Yoshinox BB”, “Yoshinox 2246G”, “Yoshinox 425”, “Yoshinox 250”, “Yoshinox 930”, “Yoshinox SS”, “Yoshinox TT”, “Yoshinox 917”, “Yoshinox 314” ( As above, API Corporation) and the like can be mentioned.

  [C] Antioxidants include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris- (3) among compounds having a hindered phenol structure. , 5-Di-tert-butyl-4-hydroxybenzyl) -isocyanurate is preferred.

  [C] The content of the antioxidant is usually 15 parts by mass or less, preferably 0.1 parts by mass or more and 10 parts by mass or less, and 0.2 parts by mass with respect to 100 parts by mass of the polymer component [A]. More preferred is 5 parts by mass or more and 5 parts by mass or less. [C] By making content of antioxidant into the said range, the cracking degradation of the insulating film formed from the said radiation sensitive resin composition can be suppressed more effectively.

<Other optional components>
In addition to the [A] polymer component, the [B] radiation sensitive acid generator, and the [C] antioxidant component, the radiation sensitive resin composition may be added as necessary as long as the effects of the present invention are not impaired. [D] Other optional components such as a polyfunctional (meth) acrylate, [E] basic compound, [F] surfactant, and [G] adhesion aid may be contained. Other optional components may be used alone or in combination of two or more. Hereinafter, each component will be described in detail.

<[D] polyfunctional (meth) acrylate>
[D] The polyfunctional (meth) acrylate can enhance the curability of the radiation-sensitive composition. The [D] polyfunctional (meth) acrylate is not particularly limited as long as it is a compound having two or more (meth) acryloyl groups. For example, an aliphatic polyhydroxy compound and (meth) acrylic acid The polyfunctional (meth) acrylate obtained by reacting, the polyfunctional (meth) acrylate modified with caprolactone, the polyfunctional (meth) acrylate modified with alkylene oxide, the (meth) acrylate having a hydroxyl group and the polyfunctional isocyanate are reacted. And a polyfunctional urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate with an acid anhydride, and the like.

  Examples of the aliphatic polyhydroxy compound include trivalent or more divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. And aliphatic polyhydroxy compounds.

  Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol dihydrate. And methacrylate.

  Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate.

  Examples of the acid anhydride include dibasic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, and biphenyltetracarboxylic acid. And dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

  Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955.

  Examples of the alkylene oxide-modified polyfunctional (meth) acrylate include, for example, ethylene oxide of bisphenol A and / or propylene oxide-modified di (meth) acrylate, ethylene oxide of isocyanuric acid and / or propylene oxide-modified tri (meth) acrylate. , Ethylene oxide and / or propylene oxide modified tri (meth) acrylate of trimethylolpropane, ethylene oxide and / or propylene oxide modified tri (meth) acrylate of pentaerythritol, ethylene oxide and / or propylene oxide modified tetra (meth) of pentaerythritol ) Ethylene oxide and / or propylene oxide modified penta (meth) acrylate of acrylate and dipentaerythritol Over DOO, ethylene oxide dipentaerythritol and / or propylene oxide-modified hexa (meth) acrylate.

  Among these polyfunctional (meth) acrylates, polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, polyfunctional (meth) acrylates modified with caprolactone Polyfunctional urethane (meth) acrylate and polyfunctional (meth) acrylate having a carboxyl group are preferred. Among polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, di Among the polyfunctional (meth) acrylates in which pentaerythritol hexaacrylate is a carboxyl group, a compound obtained by reacting pentaerythritol triacrylate and succinic anhydride, dipentaerythritol pentaacrylate and succinic anhydride are reacted. The compound obtained in this way is particularly preferred from the viewpoint of good alkali developability.

  [D] Polyfunctional (meth) acrylates may be used alone or in combination of two or more.

  [D] The content of the polyfunctional (meth) acrylate is preferably 1 part by mass or more and 100 parts by mass or less, and more preferably 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polymer component [A]. . [D] By making content of polyfunctional (meth) acrylate into the said range, while being able to raise the hardness of a cured film more, the radiation sensitivity of the said radiation sensitive resin composition can be raised more.

<[E] basic compound>
[E] The basic compound can be arbitrarily selected from those used in chemically amplified resists. The radiation-sensitive resin composition contains [E] a basic compound, so that the diffusion length of the acid generated from the [B] radiation-sensitive acid generator by exposure can be appropriately controlled. Can be improved.

  [E] Examples of basic compounds include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, carboxylic acid quaternary ammonium salts, and the like. These [E] basic compounds may be used alone or in combination of two or more.

[Aliphatic amine]
Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and dicyclohexylamine. , Dicyclohexylmethylamine and the like.

[Aromatic amine]
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.

[Heterocyclic amine]
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4,3,0] -5-nonene, 1,8-diazabicyclo [5,3,0] -7 -Undecene and the like.

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

[Carboxylic acid quaternary ammonium salt]
Examples of the carboxylic acid quaternary ammonium salt include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

  Among these, the [E] basic compound is preferably a heterocyclic amine, such as 4-dimethylaminopyridine, 4-methylimidazole, 1,5-diazabicyclo [4,3,0] -5-nonene, dimethyl. n-dodecylamine, 2-phenylbenzimidazole and the like are more preferable.

  [E] The content of the basic compound is usually 2 parts by mass or less with respect to 100 parts by mass of the polymer component [A], preferably 0.001 to 1 part by mass, and 0.005 parts by mass. More preferred is at least 0.2 part by weight. [E] By making content of a basic compound into the said range, pattern developability improves more.

<[F] Surfactant>
[F] Surfactant is a component which improves the film-forming property of the said radiation sensitive resin composition. The radiation-sensitive resin composition can improve the surface smoothness of the coating film by containing [F] surfactant, and as a result, the film thickness of the insulating film formed from the radiation-sensitive resin composition. Uniformity can be further improved.

  Examples of [F] surfactants include fluorine-based surfactants and silicone-based surfactants. These [F] surfactants may be used alone or in combination of two or more.

  As the fluorosurfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group at at least one of the terminal, main chain and side chain is preferable. For example, 1,1,2,2-tetrafluoro n- Octyl (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 di (1,1,2,2-tetrafluoro n-butyl) ether, hexapropylene glycol di (1,1,2,2,3,3) -Hexafluoro n-pentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluoro n-butyl) ether, Sodium fluoro 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, sodium fluoroalkylcarboxylate, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkylammonium iodide, fluoroalkylbetaine, fluoroalkylpolyoxyethylene ether, Fluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, carboxylic acid fluoroalkyl ester and the like can be mentioned.

Examples of commercially available fluorosurfactants include:
“BM-1000”, “BM-1100” (above, BM CHEMIE), “Megafuck F142D”, “Megafuck F172”, “Megafuck F173”, “Megafuck F183”, “Megafuck F178”, “ “Megafuck F191”, “Megafuck F471”, “Megafuck F476” (above, Dainippon Ink & Chemicals, Inc.);
“FLORAD FC-170C”, “FLORARD FC-171”, “FLORARD FC-430”, “FLORARD FC-431” (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 "(Asahi Glass Co., Ltd.);
"F Top EF301", "F Top EF303", "F Top EF352" (the above, Shin-Akita Kasei Co., Ltd.);
"Factent FT-100", "Factent FT-110", "Factent FT-140A", "Factent FT-150", "Factent FT-250", "Factent FT-251", "Gent FT-300", "left FT-310", "after FT-400S", "after FTTX-218", "after FT-251" (hereinafter referred to as Neos).

Examples of commercially available silicone surfactants include:
“Tore Silicone DC3PA”, “Tore Silicone DC7PA”, “Tore Silicone SH11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Tore Silicone SH29PA”, “Tore Silicone SH30PA”, “Tore Silicone SH-190”, “Tore Silicone SH-193”, “Tore Silicone SZ-6032”, “Tore Silicone SF-8428”, “Tore Silicone DC-57”, “Tore Silicone DC-190”, “SH 8400 FLUID” (above, Toray Dow Corning Silicone);
“TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4446”, “TSF-4460”, “TSF-4442” (hereinafter, GE Toshiba Silicone);
“Organosiloxane polymer KP341” (Shin-Etsu Chemical Co., Ltd.) and the like.

  [F] The content of the surfactant is usually 3 parts by mass or less, preferably 0.01 parts by mass or more and 2 parts by mass or less, and 0.05 parts by mass with respect to 100 parts by mass of the polymer component [A]. More preferred is 1 part by weight or more and 1 part by weight or less. [F] By making content of surfactant into the said range, the film thickness uniformity of the coating film formed can be improved more.

<[G] Adhesion aid>
[G] Adhesion aid is a component that improves the adhesion between the film forming object such as a substrate and the insulating film. [G] The adhesion aid is particularly useful for improving the adhesion between the inorganic substrate and the insulating film. Examples of the inorganic substance include silicon compounds such as silicon, silicon oxide, and silicon nitride, and metals such as gold, copper, and aluminum.

  [G] As the adhesion assistant, a functional silane coupling agent is preferable. Examples of the functional silane coupling agent include a silane coupling agent having a reactive substituent such as a carboxy group, a methacryloyl group, an isocyanate group, an epoxy group (preferably an oxiranyl group), and a thiol group. These [G] adhesion assistants may be used alone or in combination of two or more.

  Examples of functional silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and γ-glycidoxypropyl. Examples include trimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. Among these, as the functional silane coupling agent, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-Methacryloxypropyltrimethoxysilane is preferred.

  [G] The content of the adhesion assistant is usually 30 parts by mass or less, preferably 0.5 parts by mass or more and 20 parts by mass or less, and 1 part by mass or more with respect to 100 parts by mass of the polymer component [A]. 10 parts by mass or less is more preferable. [G] By setting the content of the adhesion assistant in the above range, the adhesion between the insulating film and the substrate is further improved.

<Method for preparing radiation-sensitive resin composition>
The radiation-sensitive resin composition was dissolved or dispersed by mixing a [A] polymer component, [B] a radiation-sensitive acid generator, a suitable component as necessary, and other optional components in a solvent. Prepared to a state.

  As the [A] polymer component, those containing [A1] polymer and [A2] polymer having different carboxyl group protection rates in a predetermined ratio are used. That is, the preparation method includes a step of blending the [A1] polymer and the [A2] polymer. [A] The mass ratio of the [A1] polymer and the [A2] polymer in the polymer component is usually from 1/99 to 99/1, preferably from 30/70 to 70/30, 40/60. 60/40 or more is more preferable, and 45/55 or more and 55/45 or less is more preferable.

[solvent]
As the solvent, a solvent that uniformly dissolves or disperses other components in the radiation-sensitive resin composition and does not react with the other components is preferably used. Examples of such solvents include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, Aromatic hydrocarbons, ketones, other esters and the like can be mentioned.

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

  Examples of the ethers include tetrahydrofuran.

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

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

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

  Examples of the propylene glycol monoalkyl ether acetate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate 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. Can be mentioned.

  Examples of the aromatic hydrocarbons include toluene and xylene.

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

  Examples of the other esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, and ethyl 2-hydroxy-2-methylpropionate. , Methyl hydroxyacetate, ethyl hydroxyacetate, hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3-hydroxypropion Acid butyl, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, , Methyl propoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propylbutoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2- Propyl methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butoxy Ethyl propionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, -Butyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3- Examples include propyl propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

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

<Insulating film of display element>
The insulating film of the display element of the present invention is formed from the radiation sensitive resin composition. Since the insulating film is formed from the radiation-sensitive resin composition, it has excellent adhesion to a substrate or the like. The insulating film having such characteristics can be used as an interlayer insulating film, a planarizing film, a bank (partition) defining a region for forming a light emitting layer, a spacer, a protective film, a color filter coloring pattern, or the like. Can be used. Note that a method for forming the insulating film is not particularly limited, but an insulating film forming method described below is preferably applied.

<Method for forming insulating film of display element>
The method for forming an insulating film of the present invention includes a step of forming a coating film on a substrate (hereinafter also referred to as “step (1)”), a step of irradiating at least a part of the coating film (hereinafter referred to as “step”). (Also referred to as “(2)”), a step of developing the coating film irradiated with radiation (hereinafter also referred to as “step (3)”), and a step of heating the developed coating film (hereinafter referred to as “step (4)”). ”).

  According to the insulating film forming method, an insulating film having high pattern shape stability can be formed. In addition, since the amount of change in the film thickness of the unexposed portion can be suppressed, the production process margin can be improved as a result, and the yield can be improved. Furthermore, by forming a pattern by exposure, development, and heating using photosensitivity, an insulating film for a display element having a fine and elaborate pattern can be easily formed.

[Step (1)]
In this step, the radiation sensitive resin composition is applied onto a substrate to form a coating film. When the said radiation sensitive resin composition contains a solvent, it is preferable to remove a solvent by prebaking an application surface.

  Examples of the substrate include glass, quartz, silicone, and resin. Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, a ring-opening polymer of 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, but are usually about 70 to 120 ° C. and about 1 to 10 minutes.

[Step (2)]
In this step, at least a part of the coating film is irradiated with radiation and exposed. When exposing, it exposes normally through the photomask which has a predetermined pattern. As the radiation used for exposure, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation containing ultraviolet light of 365 nm is more preferable. The exposure amount ^is preferably ^{500J / m 2 ~6,000J / m 2} , 1,500J / m 2 ~1,800J / m 2 is more preferable. This exposure amount is a value obtained by measuring the intensity of radiation at a wavelength of 365 nm with an illuminometer (“OAI model 356” manufactured by OAI Optical Associates).

[Step (3)]
In this step, the coating film irradiated with radiation is developed. By developing the coated film after exposure, unnecessary portions (radiation irradiated portions) are removed to form a predetermined pattern.

  The developer used in this step is preferably an alkaline aqueous solution. Examples of the alkali include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; and quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. . As the developer, an organic solvent such as a ketone organic solvent or an alcohol organic solvent can be used.

  An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, or a surfactant can be added to the alkaline aqueous solution. As a density | concentration of the alkali in aqueous alkali solution, from a viewpoint of obtaining suitable developability, 0.1 to 5 mass% is preferable.

  Examples of the developing method include a liquid piling method, a dipping method, a rocking dipping method, a shower method, and the like. The development time varies depending on the composition of the radiation sensitive resin composition, but is usually about 10 seconds to 180 seconds.

  Following such development processing, for example, washing with running water is performed for 30 seconds to 90 seconds, and then a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen.

  It is preferable that the film thickness change rate of the film thickness after development with respect to the film thickness of the coating film before development is 90% or more. As described above, according to the forming method using the radiation-sensitive resin composition, the amount of change in the film thickness of the unexposed portion with respect to the development time can be suppressed, and the film thickness after development is 90% of the film thickness before development. % Or more can be maintained.

[Step (4)]
In this step, the developed coating film is heated. For heating, a heating device such as a hot plate or an oven is used to heat the patterned thin film, whereby the curing reaction of the polymer component [A] can be promoted to form an insulating film. As heating temperature, it is about 120 to 250 degreeC, for example. The heating time varies depending on the type of the heating device, but is, for example, about 5 to 30 minutes for a hot plate and about 30 to 90 minutes for an oven. Moreover, the step baking method etc. which perform a heating process 2 times or more can also be used. In this way, a patterned thin film corresponding to the target insulating film can be formed on the surface of the substrate. The thickness of this insulating film is preferably 0.1 μm to 8 μm, and more preferably 0.1 μm to 6 μm.

<Display element>
The display element of the present invention includes the insulating film. The display element is, for example, a liquid crystal display element, an organic EL display element, or the like.

  The liquid crystal display element is composed of, for example, a liquid crystal cell, a polarizing plate, and the like. Since the liquid crystal display element includes the insulating film, the liquid crystal display element is excellent in reliability such as light resistance and adhesion of the insulating film to a substrate or the like.

  As a method for manufacturing a display element, first, a pair (two) of transparent substrates having a transparent conductive film (electrode) on one side is prepared, and the radiation-sensitive resin composition is formed on the transparent conductive film of one of the substrates. In accordance with the method described in the above <Insulating film formation method>, an insulating film such as an interlayer insulating film, a spacer, or a protective film is formed. Next, an alignment film having liquid crystal alignment ability is formed on the transparent conductive film and the spacer or protective film of these substrates. These substrates are arranged facing each other with a certain gap (cell gap) so that the liquid crystal alignment direction of each alignment film is orthogonal or antiparallel, with the surface on which the alignment film is formed inside. A liquid crystal is filled in the cell gap defined by the surface of the substrate (alignment film) and the spacer, and the filling hole is sealed to constitute a liquid crystal cell. Then, the polarizing plate is bonded to both outer surfaces of the liquid crystal cell so that the polarization direction thereof coincides with or orthogonal to the liquid crystal alignment direction of the alignment film formed on one surface of the substrate. The liquid crystal display element can be obtained.

  As another method for manufacturing a liquid crystal display element, a pair of transparent substrates on which a transparent conductive film, an insulating film such as an interlayer insulating film, a protective film, and a spacer and an alignment film are formed are prepared in the same manner as the above manufacturing method. . After that, along the edge of one of the substrates, an ultraviolet curable sealant is applied using a dispenser, then the liquid crystal is dropped into a fine droplet using a liquid crystal dispenser, and the two substrates are bonded together under vacuum. Do. Then, both the substrates are sealed by irradiating the sealing agent part with ultraviolet rays using a high-pressure mercury lamp. Finally, a liquid crystal display element as a display element of the present invention is obtained by attaching polarizing plates to both outer surfaces of the liquid crystal cell.

  Examples of the liquid crystal used in the above-described method for manufacturing a liquid crystal display element include nematic liquid crystal and smectic liquid crystal. In addition, as a polarizing plate used outside the liquid crystal cell, a polarizing film in which a polarizing film called an “H film” that absorbs iodine while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films, or an H film Examples thereof include a polarizing plate made of itself.

  On the other hand, in the organic electroluminescence element, the insulating film formed from the radiation-sensitive resin composition can be used as a planarization film formed on the TFT element, a partition defining a light emitting site, or the like.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to a following example. In addition, the weight average molecular weight (Mw) of the [A1] polymer and the [A2] polymer was measured by the following method.

[Weight average molecular weight (Mw)]
The weight average molecular weight (Mw) was measured under the following conditions by gel permeation chromatography (GPC).
Equipment: “GPC-101” from Showa Denko
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined Mobile phase: Tetrahydrofuran Column temperature: 40 ° C
Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene

<Synthesis of [A1] polymer or [A2] polymer>
[Synthesis Example 1] (Synthesis of polymer (A-1) having a protection rate of 5 mol%)
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a radical polymerization initiator and 200 parts by mass of diethylene glycol ethyl methyl ether as a solvent. Subsequently, 20 parts by mass of methacrylic acid giving structural unit (I), 7 parts by mass of methacrylic acid protected with a tetrahydropyranyl group giving structural unit (II), and 3,4-epoxytricyclo giving structural unit (III) [5.2.1.0 ^2.6 ] After 41 parts by mass of decyl acrylate and 22 parts by mass of methyl methacrylate and 10 parts by mass of hydroxyethyl methacrylate to give other structural units were charged with nitrogen, the mixture was gently stirred. I started. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing a polymer (A-1) having a carboxyl group protection rate of 5% (mass basis). The polymer (A-1) had a polystyrene equivalent weight average molecular weight (Mw) of 10,000. Moreover, the solid content concentration of the polymer solution obtained here was 33.0 mass%.

[Synthesis Example 2] (Synthesis of polymer (A-2) having a protection ratio of 10 mol%)
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a radical polymerization initiator and 200 parts by mass of diethylene glycol ethyl methyl ether as a solvent. Subsequently, 27 parts by weight of methacrylic acid giving structural unit (I), 13 parts by weight of methacrylic acid protected with a tetrahydropyranyl group giving structural unit (II), 3-methacryloyloxymethyl-3 giving structural unit (III) -After 50 parts by mass of ethyloxetane and 10 parts by mass of hydroxyethyl methacrylate giving other structural units were charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing a polymer (A-2) having a carboxyl group protection rate of 10% (mass basis). The polymer (A-2) had a weight average molecular weight (Mw) in terms of polystyrene of 10,000. Moreover, the solid content concentration of the polymer solution obtained here was 31.2 mass%.

[Synthesis Example 3] (Synthesis of polymer (A-3) having a protection rate of 20 mol%)
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a radical polymerization initiator and 200 parts by mass of diethylene glycol ethyl methyl ether as a solvent. Subsequently, 15 parts by weight of methacrylic acid giving structural unit (I), 26 parts by weight of methacrylic acid protected with a tetrahydropyranyl group giving structural unit (II), 3-methacryloyloxymethyl-3 giving structural unit (III) -After 50 parts by mass of ethyloxetane and 9 parts by mass of hydroxyethyl methacrylate giving other structural units were charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing a polymer (A-3) having a carboxyl group protection rate of 20% (mass basis). The polymer (A-3) had a weight average molecular weight (Mw) in terms of polystyrene of 10,000. Moreover, the solid content concentration of the polymer solution obtained here was 31.2 mass%.

[Synthesis Example 4] (Synthesis of polymer (A-4) having a protection ratio of 50 mol%)
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a radical polymerization initiator and 200 parts by mass of diethylene glycol ethyl methyl ether as a solvent. Subsequently, 10 parts by weight of methacrylic acid giving structural unit (I), 65 parts by weight of methacrylic acid protected with a tetrahydropyranyl group giving structural unit (II), and 3,4-epoxycyclohexylmethyl giving structural unit (III) After 15 parts by weight of methacrylate and 5 parts by weight of methyl methacrylate and 5 parts by weight of hydroxyethyl methacrylate giving other structural units were charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing a polymer (A-4) having a carboxyl group protection rate of 50% (mass basis). The polystyrene equivalent weight average molecular weight (Mw) of the polymer (A-4) was 9,000. Moreover, the solid content concentration of the polymer solution obtained here was 31.2 mass%.

[Synthesis Example 5] (Synthesis of polymer (A-5) having a protection ratio of 75 mol%)
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a radical polymerization initiator and 200 parts by mass of diethylene glycol ethyl methyl ether as a solvent. Subsequently, 0.5 part by weight of methacrylic acid giving structural unit (I), 99 parts by weight of methacrylic acid protected with tetrahydropyranyl group giving structural unit (II), 3,4-epoxy giving structural unit (III) After 0.5 parts by mass of tricyclo [5.2.1.0 ^2.6 ] decyl acrylate was charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing a polymer (A-5) having a carboxyl group protection rate of 90% (mass basis). The polymer (A-5) had a weight average molecular weight (Mw) in terms of polystyrene of 10,000. Moreover, the solid content concentration of the polymer solution obtained here was 31.5 mass%.

[Comparative Synthesis Example 1] (Synthesis of polymer (a-1) having a protection rate of 100 mol%)
In Comparative Synthesis Example 1, among the structural unit (I) and the structural unit (II), the polymer (a) as a comparative [a] polymer containing only the structural unit (II) and not containing the structural unit (I) (a -1) was synthesized.
Specifically, in a flask equipped with a condenser and a stirrer, 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a radical polymerization initiator and 200 parts by mass of diethylene glycol ethyl methyl ether as a solvent Was charged. Subsequently, 100 parts by weight of methacrylic acid protected with a tetrahydropyranyl group giving the structural unit (II) was charged, and the atmosphere was replaced with nitrogen. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (a-1) having a carboxyl group protection rate of 100% (mass basis). The polymer (a-1) had a polystyrene equivalent weight average molecular weight (Mw) of 11,000. Moreover, the solid content concentration of the polymer solution obtained here was 31.0 mass%.

[Comparative Synthesis Example 2] (Synthesis of polymer (a-2) having a protection rate of 0%)
In Comparative Synthesis Example 1, among the structural unit (I) and the structural unit (II), the polymer (a) as a comparative [a] polymer containing only the structural unit (I) and not the structural unit (II) (a -2) was synthesized.
Specifically, in a flask equipped with a condenser and a stirrer, 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a radical polymerization initiator and 200 parts by mass of diethylene glycol ethyl methyl ether as a solvent Was charged. Subsequently, 20 parts by weight of methacrylic acid giving structural unit (I), 50 parts by weight of 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate giving structural unit (III), and other After 20 parts by mass of methyl methacrylate and 10 parts by mass of styrene giving structural units were charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing a polymer (a-2) having a carboxyl group protection rate of 0% (mass basis). The polymer (a-2) had a polystyrene equivalent weight average molecular weight (Mw) of 10,000. Moreover, the solid content concentration of the polymer solution obtained here was 31.5 mass%.

<Preparation of radiation-sensitive resin composition>
The radiation sensitive resin composition was prepared to the composition shown in Table 1. The [A] polymer component, [B] radiation sensitive acid generator, [C] antioxidant, [D] polyfunctional (meth) acrylate, and [E] basic compound of Table 1 are as shown below. It is.

[[A] Polymer component ([A1] polymer, [A2] polymer, [a] polymer])
A-1: Polymer (A-1) synthesized in Synthesis Example 1 and having a protection rate of 5%
A-2: a polymer having a protection rate of 10% synthesized in Synthesis Example 2 (A-2)
A-3: Polymer with a protection rate of 20% synthesized in Synthesis Example 3 (A-3)
A-4: Polymer (A-4) synthesized in Synthesis Example 4 and having a protection rate of 50%
A-5: Polymer synthesized in Synthesis Example 5 and having a protection rate of 90% (A-5)
a-1: Polymer (a-1) synthesized in Comparative Synthesis Example 1 and having a protection rate of 100%
a-2: Polymer with a protection rate of 0% synthesized in Comparative Synthesis Example 2 (a-2)

Ｂ−５：下記式（Ｂ−５）で表されるスルホン酸誘導体化合物

[[B] Radiation sensitive acid generator]
B-1: 5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (“IRGACURE PAG 103” from BASF)
B-2: (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (“IRGACURE PAG 121” from BASF)
B-3: (5-octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile (“CGI-725” from BASF)
B-4: An oxime sulfonate compound represented by the following formula (B-4) ("IRGACURE PAG 203" from BASF)

B-5: A sulfonic acid derivative compound represented by the following formula (B-5)

Ｃ−３：下記式（Ｃ−３）で表されるＡＤＥＫＡ社の「アデカスタブＡＯ−７０」

[[C] Antioxidant]
C-1: 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenol) butane (“ADEKA STAB AO-30” from ADEKA)
C-2: “ADEKA STAB AO-60” of ADEKA Corporation represented by the following formula (C-2)

C-3: “ADEKA STAB AO-70” of ADEKA Corporation represented by the following formula (C-3)

[D] Multifunctional (meth) acrylate D-1: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (“KAYARAD DPHA” by Nippon Kayaku Co., Ltd.)
D-2: Succinic acid-modified pentaerythritol triacrylate (“Aronix TO-756” manufactured by Toagosei Co., Ltd.)
D-3: Trimethylolpropane triacrylate

[E] Basic compound E-1: 2-Dimethylaminopyridine E-2: 2-Phenylbenzimidazole

[Example 1]
The amount corresponding to 50 parts by mass (solid content) and 50 parts by mass (solid content) of (A-1) polymer solution (A-1) and polymer (A-2) ) Was mixed with 5 parts by mass of a radiation sensitive acid generator (B-1) and filtered through a membrane filter having a pore size of 0.2 μm to prepare a radiation sensitive resin composition.

[Examples 2 to 6 and Comparative Examples 1 and 2]
A radiation-sensitive resin composition was prepared in the same manner as in Example 1 except that the components having the types and contents shown in Table 1 were used. In addition, "-" in Table 1 indicates that the corresponding component was not blended.

<Evaluation>
The radiation sensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 and 2 were evaluated for radiation sensitivity, storage stability, light resistance, transmittance, and pattern adhesion according to the following methods. The evaluation results are shown in Table 2.

[Evaluation of radiation sensitivity]
A radiation sensitive resin composition was applied onto a glass substrate using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. Subsequently, using an exposure machine (Canon's “MPA-600FA (ghi line mixing)”), the exposure amount to the coating film through a mask having a 60 μm line and space (10 to 1) pattern. Was irradiated as a variable. Then, it developed by the piling method for 80 seconds at 25 degreeC with 0.5 mass% tetramethylammonium hydroxide aqueous solution. Next, washing with running ultrapure water for 1 minute was performed, followed by drying to form a pattern on the chromium-deposited glass substrate after the HMDS treatment. At this time, the amount of exposure necessary to completely dissolve the 6 μm space pattern was examined. When the exposure value is 500 (J / m ² ) or less, it can be determined that the sensitivity is good.

[Evaluation of storage stability]
The radiation-sensitive composition solution was left in an oven at 40 ° C. for 1 week, and the viscosity before and after being placed in the oven was measured to determine the rate of change in viscosity (%). At this time, when the viscosity change rate is 5% or less, the storage stability is good, and when it exceeds 5%, the storage stability is poor.

[Evaluation of light resistance]
A radiation sensitive resin composition was applied onto a silicon substrate using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. This silicon substrate was heated in a clean oven at 220 ° C. for 1 hour to obtain an insulating film. Each insulating film obtained was irradiated with 800,000 J / m ² at an illuminance of 130 mW by a UV irradiation apparatus (“UVX-02516S1JS01” manufactured by Ushio Inc.). When the film thickness after irradiation is 3.5% or less compared to the film thickness before irradiation, the light resistance of the insulating film is good, and the film thickness reduction is 3.5%. If it is less than that, it can be said that the light resistance of the insulating film is poor.
In the light resistance evaluation, since the patterning of the insulating film to be formed is unnecessary, the development process was omitted, and only the coating film forming process, the light resistance test, and the heating process were performed for evaluation.

[Evaluation of transmittance]
Similar to the light resistance evaluation, a coating film was formed on a silicon substrate using the radiation-sensitive resin composition. This silicon substrate was heated in a clean oven at 220 ° C. for 1 hour to form an insulating film. About this insulating film, the transmittance | permeability in wavelength 400nm was measured using the spectrophotometer ("150-20 type double beam" by Hitachi, Ltd.). At this time, it can be said that the transparency is good when the transmittance is 90% or more, and the transparency is poor when the transmittance is less than 90%.

[Evaluation of pattern adhesion]
The adhesion of the pattern was evaluated after exposure. Specifically, first, a radiation sensitive resin composition is applied onto a glass substrate using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. did. Subsequently, 700 (J / m ² ) was passed through a mask having a 10 μm line-and-space (one-to-one) pattern using an exposure machine (“MPA-600FA (ghi line mixing)” manufactured by Canon Inc.). ). Thereafter, it was left in a clean room for 1 hour, and then developed with a 0.5 mass% aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 80 seconds. Next, running water was washed with ultrapure water for 1 minute, and then dried to form a pattern on the glass substrate. The substrate after development was observed with an optical microscope to confirm the presence or absence of pattern peeling. The criteria for determining pattern adhesion are shown below.

When pattern peeling is hardly seen: “○”
When pattern peeling is slightly seen: “△”
When the pattern is peeled off and almost no pattern remains on the substrate: “×”

  As is clear from the results in Table 2, the radiation-sensitive resin compositions of Examples 1 to 6 were excellent in radiation sensitivity, storage stability, light resistance, transmittance, and pattern adhesion. In contrast, the radiation-sensitive compositions of Comparative Examples 1 and 2 did not give good results with respect to radiation sensitivity, storage stability, light resistance, transmittance, and pattern adhesion.

  The present invention provides a radiation-sensitive resin composition for forming an insulating film of a display element that sufficiently satisfies general characteristics such as radiation sensitivity, is excellent in storage stability, and can reduce poor adhesion of an insulating film. Can be provided. The present invention further provides a method for preparing the radiation-sensitive resin composition, an insulating film for a display element formed from the radiation-sensitive resin composition, a method for forming the same, and a display element including the insulating film. it can. Therefore, the radiation-sensitive resin composition, the method for preparing the radiation-sensitive resin composition, the insulating film, the method for forming the insulating film, and the display element are preferably used for manufacturing processes of liquid crystal display devices and the like. Can do.

Claims (9)

A first polymer having at least the second structural unit of a first structural unit containing a carboxyl group and a second structural unit in which the carboxyl group is protected by a protecting group, and a third structural unit containing a crosslinkable group;
A second polymer having at least the first structural unit of the first structural unit and the second structural unit and the third structural unit, and a radiation-sensitive acid generator,
The first protection rate which is the molar ratio of the second structural unit in the total number of moles of the first structural unit and the second structural unit in the first polymer, and the molar ratio in the second polymer. Ri difference 5 mol% to 70 mol% der following there second protection rate,
The third structural unit, the insulating film-forming radiation sensitive resin composition of the represented Ru display device by the following formula (3).

(In formula (3), R ¹¹ is .R ¹² at least part of the hydrogen atoms are group substituted with a hydroxyl group in which a hydrogen atom, an alkyl group or the alkyl group having 1 to 4 carbon atoms having the following It is a group represented by the formula (4-1) or the following formula (4-2): X ¹ is a single bond, a methylene group or an alkylene group having 2 to 12 carbon atoms, Y ¹ is a single bond, An oxygen atom, a sulfur atom or an imino group.)

The radiation-sensitive resin for forming an insulating film of a display element according to claim 1, wherein the structure in which the carboxyl group in the second structural unit is protected by a protective group is represented by the following formula (1) or the following formula (2). Composition.

(In Formula (1), R ¹ and R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or at least a part of the hydrogen atoms of the hydrocarbon group is a hydroxyl group or a halogen atom. Or a group substituted with a cyano group, provided that R ¹ and R ² are not both hydrogen atoms, R ³ is a hydrocarbon group having 1 to 30 carbon atoms, carbon-carbon of this carbon hydrogen group Or a group containing an oxygen atom at the end of the bond side or at least part of the hydrogen atoms of these groups is a group substituted with a hydroxyl group, a halogen atom or a cyano group.
In formula (2), R ^{4 to} R ¹⁰ are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. n is 1 or 2. When n is 2, the plurality of R ⁷ and R ⁸ may be the same or different. ) The radiation sensitive resin composition for insulating film formation of the display element of Claim 1 or Claim 2 in which the said radiation sensitive acid generator contains the oxime sulfonate group represented by following formula (5).

(In Formula (5), R ¹³ is an alkyl group, a monovalent alicyclic hydrocarbon group, an aryl group, or a group in which at least a part of hydrogen atoms of these groups is substituted with a substituent.) The radiation sensitive resin composition for insulating film formation of the display element of Claim 1, 2 or 3 which further contains antioxidant. The radiation-sensitive resin composition for forming an insulating film of a display element according to claim 4 , wherein the antioxidant is a compound having a hindered phenol structure. A first polymer having at least the second structural unit of a first structural unit containing a carboxyl group and a second structural unit in which the carboxyl group is protected by a protecting group, and a third structural unit containing a crosslinkable group; And blending a second polymer having at least the first structural unit of the first structural unit and the second structural unit and the third structural unit,
The first protection rate which is the molar ratio of the second structural unit in the total number of moles of the first structural unit and the second structural unit in the first polymer, and the molar ratio in the second polymer. Ri difference 5 mol% to 70 mol% der following there second protection rate,
Process for the preparation of the third structural unit, the insulating film-forming radiation sensitive resin composition of the display device you express the following formula (3).

(In formula (3), R ¹¹ is .R ¹² at least part of the hydrogen atoms are group substituted with a hydroxyl group in which a hydrogen atom, an alkyl group or the alkyl group having 1 to 4 carbon atoms having the following It is a group represented by the formula (4-1) or the following formula (4-2): X ¹ is a single bond, a methylene group or an alkylene group having 2 to 12 carbon atoms, Y ¹ is a single bond, An oxygen atom, a sulfur atom or an imino group.)

The insulating film of the display element formed from the radiation sensitive resin composition for insulating film formation of the display element of any one of Claims 1-5 . Insulating film comprising a step of forming a coating film on a substrate, a step of irradiating at least a part of the coating film, a step of developing the coating film irradiated with radiation, and a step of heating the developed coating film A forming method of
The formation method of the insulating film of a display element using the radiation sensitive resin composition for insulating film formation of the display element of any one of Claims 1-5 for formation of the said coating film. A display element comprising the insulating film according to claim 7 .