JP2018151621A - Method for producing cured film for display elements, radiation-sensitive resin composition, cured film for display elements and display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a cured film for liquid crystal display elements that makes it possible to obtain a cured film having reduced uneven exposure from multiple exposure, and a radiation-sensitive resin composition, and a cured film for display elements having reduced uneven exposure from multiple exposure, and a display element including such a cured film for display elements.SOLUTION: A method for producing a cured film for display elements includes the steps of: using a radiation-sensitive resin composition to form a coating on a substrate; subjecting at least part of the coating to multiple exposure; and developing the coating. The radiation-sensitive resin composition contains a polymer having an ionic polymerizable group, and at least one selected from a photoacid generator and a photo-base generator.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a cured film for a display element, a radiation sensitive resin composition, a cured film for a display element, and a display element.

Generally, a cured film such as an interlayer insulating film is used for a display element such as a liquid crystal display element. The display element cured film is required to have high surface hardness, high light transmittance, and excellent chemical resistance.

  As a material for forming such a cured film for a display element, a radiation-sensitive resin composition is widely used because the number of steps for forming a predetermined pattern is small and high surface hardness is obtained ( JP, 2001-354822, A). These radiation-sensitive resin compositions generally require properties such as high sensitivity and resolution, little residue after development, and high adhesion during development.

  Formation of the cured film using the radiation-sensitive resin composition is performed by forming a coating film on the substrate using the radiation-sensitive resin composition, exposing the coating film, and developing the exposed coating film. Is done. As an apparatus for exposure, a projection exposure apparatus that irradiates a coating film on a substrate with radiation from a light source through a photomask and a lens is used. On the other hand, in recent years, the area of display elements has been increased, and accordingly, it is desired to expand the exposure area in the exposure apparatus. Therefore, in the above projection exposure apparatus, a scanning exposure apparatus has been developed and put into practical use (Japanese Patent Laid-Open Nos. 6-120108, 1-229819, 61-164126, 7). No. -153683, JP 10-92729 A, JP 2010-135479 A, JP 2013-142890 A). In such a scanning exposure apparatus, since the exposure range in one scan is wide, a large-sized substrate can be exposed at high speed, and the productivity of the display element can be increased. However, when such a scanning exposure apparatus is used, the total exposure amount in the multiple exposure portion and other portions (portions for only one exposure), where a portion that is exposed to irradiation light multiple times may occur. Even if there is no difference, exposure unevenness may occur.

JP 2001-354822 A JP-A-6-120108 JP-A-1-298719 JP 61-164126 A JP-A-7-153683 JP-A-10-92729 JP 2010-135479 A JP 2013-142890 A

  The present invention has been made based on the circumstances as described above, and an object thereof is a method for producing a cured film for a liquid crystal display element capable of obtaining a cured film with reduced exposure unevenness due to multiple exposure, and It is an object to provide a radiation-sensitive resin composition, a cured film for display elements in which uneven exposure due to multiple exposure is reduced, and a display element including such a cured film for display elements.

  The invention made in order to solve the above problems includes a step of forming a coating film on a substrate using a radiation-sensitive resin composition, a step of multiply exposing at least a part of the coating film, and developing the coating film. A process for producing a cured film for a display element, wherein the radiation-sensitive resin composition comprises a polymer having an ion polymerizable group and at least one selected from a photoacid generator and a photobase generator. is there.

  Another invention made to solve the above-mentioned problems is used in the manufacture of a cured film for a display element by multiple exposure to at least a part, a polymer having an ion polymerizable group, a photoacid generator and light. A radiation-sensitive resin composition for display elements, comprising at least one selected from base generators.

  Yet another invention made to solve the above problems is a cured film for a display element, which is a cured product of the radiation-sensitive resin composition.

  Still another invention made in order to solve the above-mentioned problems is a display element provided with a cured film for a display element.

  The present invention provides a method for producing a cured film for a liquid crystal display element and a radiation-sensitive resin composition capable of obtaining a cured film with reduced exposure unevenness due to multiple exposure, and exposure unevenness due to multiple exposure. The display element cured film and the display element including such a display element cured film can be provided. Therefore, according to the present invention, even when a part of the region on the substrate is subjected to multiple exposure and a pattern or the like is formed in the region, the exposure unevenness in the multiple exposure portion can be reduced, and photolithography for a large substrate can be performed. It can be used suitably for the manufacturing process of a display element etc., such as a process.

  Hereinafter, a radiation-sensitive resin composition, a method for producing a cured film for a display element using the same, a cured film for a display element, and a display element will be described in detail in the order of embodiments of the present invention.

<Radiation sensitive resin composition>
The radiation-sensitive resin composition according to an embodiment of the present invention is used for producing a cured film for a display element by multiple exposure to at least a part, and is a polymer having an ion polymerizable group (hereinafter referred to as “[A ] Polymer ") and at least one selected from a photoacid generator and a photobase generator (hereinafter also referred to as" [B] generator "). The radiation sensitive paper resin composition is a radiation sensitive resin composition for display elements. The radiation-sensitive resin composition preferably further contains a compound having a molecular weight of 2000 or less (hereinafter also referred to as “[C] compound”) having one or more polymerizable groups in one molecule, and other Ingredients can be included.

  By having the said structure, the said radiation sensitive resin composition can obtain the cured film which was excellent in multiple exposure part stability, ie, the exposure nonuniformity resulting from multiple exposure was reduced. Moreover, the said radiation sensitive resin composition is also favorable in resolution. Further, the radiation-sensitive resin composition can be improved in sensitivity, low residue (less residue during development), development adhesion and the like by adjusting the composition.

<[A] polymer>
[A] The polymer is a polymer having an ion polymerizable group. The ion polymerizable group refers to a group that is polymerized by cationic polymerization or anionic polymerization. The ion polymerizable group may be a cationic polymerizable group or an anion polymerizable group. Examples of the ion polymerizable group include a vinyl group, a group containing a vinyl group such as a vinyloxy group (CH ₂ ═CH—O—), a group in which a hydrogen atom of the vinyl group is substituted with a substituent, a cyclic ether group, and the like. Can do. Among these, a cyclic ether group and a vinyloxy group are preferable, and a cyclic ether group is more preferable. In the case where the ion polymerizable group is a cyclic ether group, in addition to the stability of the multiple exposure part, the low residue property and the like can be effectively enhanced.

  The cyclic ether group is preferably a group containing a three-membered cyclic ether structure or a group containing a four-membered cyclic ether structure, and more preferably a group containing a three-membered cyclic ether structure.

  Specifically, an oxiranyl group (a group represented by the following formula (a)), an oxetanyl group (a group represented by the following formula (b)), a 3,4-epoxycyclohexyl group, and the following formula (2) The group represented is preferred. These cyclic ether groups may be those in which some or all of the hydrogen atoms are substituted with a substituent such as an alkyl group. Among these, as the cyclic ether group, an oxiranyl group, a 3,4-epoxycyclohexyl group, and a group represented by the following formula (2) are more preferable. By using these groups, in addition to further improving the stability of the multiple exposure part, it is possible to further improve sensitivity, resolution, low residue, development adhesion, and the like.

  In formulas (a), (b) and (2), * indicates a binding site. The group represented by the formula (2) includes an optical isomer.

  [A] The polymer preferably further contains an alicyclic hydrocarbon group having 5 to 30 carbon atoms, a phenyl group, a benzyl group, or a combination thereof. Thereby, in the cured film obtained, multiple exposure part stability increases more. The reason for this is not clear, but these relatively bulky hydrophobic cyclic structure groups fill gaps (three-dimensional areas with reduced density) in the coating film that occur during curing, which causes cure shrinkage. It is estimated that is effectively suppressed. By suppressing the curing shrinkage in this way, it is presumed that the difference in shrinkage between the portion exposed only once and the multiple exposure portion becomes smaller.

  In addition, these C5-C30 alicyclic hydrocarbon groups may be comprised only from the alicyclic structure, and may be comprised from the alicyclic structure and the chain hydrocarbon group. Examples of the chain hydrocarbon group include alkyl groups such as a methyl group and an ethyl group, alkenyl groups such as an ethenyl group, and alkynyl groups such as an ethynyl group. As the chain hydrocarbon group, an alkyl group is preferable.

Examples of the alicyclic hydrocarbon group having 5 to 30 carbon atoms include cyclopentyl group, cyclohexyl group, cycloheptanyl group, cyclooctyl group, cyclodecanyl group, cyclododecanyl group, cyclohexadecanyl group, and cycloicosane group. An alkyl group;
A cycloalkenyl group such as a cyclopentenyl group, a cyclohexenyl group, a cycloheptanyl group, a cyclooctenyl group, a cyclodecenyl group, a cyclododecenyl group;
Monovalent groups such as a norbornyl group, an isobornyl group, a dicyclopentanyl group, an adamantyl group, a bicyclo [2.2.1] hept-2-enyl group, a tricyclo [5.2.1.0 ^2.6 ] decanyl group Bridged cyclic hydrocarbon group;
And monovalent groups having a spiro ring structure such as a spirobicyclopentanyl group.

  The upper limit of the carbon number of the alicyclic hydrocarbon group is 30, but 20 is preferable, 16 is more preferable, 12 is more preferable, and 10 is more preferable. The lower limit of the carbon number of the alicyclic hydrocarbon group is 5, but it may be 6. By making the number of carbon atoms of the alicyclic hydrocarbon group not more than the above upper limit, the hydrophobicity becomes more appropriate, and the resolution, the low residue property, etc. can be particularly enhanced. On the other hand, by setting the number of carbon atoms of the alicyclic hydrocarbon group to the above lower limit or more, hydrophobicity can be improved, and stability of the multiple exposure part, development adhesion, and the like can be improved. Moreover, although the upper limit of the number of ring members (carbon number) of the alicyclic structure which the said alicyclic hydrocarbon group has is 30, 20 is preferable, 16 is more preferable, 12 is further more preferable, and 10 is still more preferable. On the other hand, the lower limit of the number of ring members is preferably 5, and more preferably 6.

  Among the alicyclic hydrocarbon group having 5 to 30 carbon atoms, phenyl group and benzyl group, an alicyclic hydrocarbon group having 5 to 30 carbon atoms is preferable, and a saturated alicyclic hydrocarbon group is more preferable.

  [A] The polymer preferably has the following structural unit (I). [A] The polymer preferably further has the following structural unit (II).

(Structural unit (I))
The structural unit (I) is a structural unit represented by the following formula (1). The structural unit (I) may be composed of only one type of structural unit or may be composed of a plurality of types of structural units.

In formula (1), R ¹ is a hydrogen atom or a methyl group. R ² is an oxiranyl group, a 3,4-epoxycyclohexyl group, a group represented by the following formula (2), an oxetanyl group, a 3-alkyloxetane-3-yl group, or a vinyloxyalkoxy group. X ¹ is a single bond, a methylene group or an alkylene group having 2 to 12 carbon atoms.

In the formula (2), * represents a bonding site with ^{X 1.} The group represented by the formula (2) includes an optical isomer.

R ¹ is a hydrogen atom or a methyl group, preferably a methyl group.

  Examples of the 3-alkyloxetane-3-yl group include 3-methyloxetane-3-yl group, 3-ethyloxetane-3-yl group, and 3-propyloxetane-3-yl group. -An ethyloxetane-3-yl group is preferred.

  Examples of the vinyloxyalkoxy group include a vinyloxymethoxy group, a vinyloxy group ethoxy group, and a vinyloxypropoxy group, and a vinyloxyethoxy group is preferable.

Among the above R ² , an oxiranyl group, a 3,4-epoxycyclohexyl group, a group represented by the above formula (2), an oxetanyl group, and a 3-alkyloxetane-3-yl group are preferable, and an oxiranyl group, 3,4 -Epoxy cyclohexyl group and the group represented by the above formula (2) are more preferable. By using these groups, in addition to further improving the stability of the multiple exposure part, it is possible to further improve sensitivity, resolution, low residue, development adhesion, and the like.

X ¹ is a single bond, a methylene group or an alkylene group having 2 to 12 carbon atoms. Examples of the alkylene group having 2 to 12 carbon atoms (alkanediyl group) include an ethylene group and a propylene group. X ¹ is preferably a single bond, a methylene group (—CH ₂ —) or an ethylene group (—CH ₂ CH ₂ —), and more preferably a methylene group.

Examples of the unsaturated compound that gives the structural unit (I) include glycidyl acrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxytricyclo [5.2.1.0]. ^2,6 ] decyl acrylate, (3-ethyloxetane-3-yl) methyl acrylate, acrylic acid ester such as 2- (vinyloxyethoxy) ethyl acrylate; glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4- Epoxy cyclohexyl methyl methacrylate, 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] decyl methacrylate, (3-ethyloxetane-3-yl) methyl methacrylate, 2- (vinyloxyethoxy) ethyl methacrylate, etc. of And methacrylic acid esters. The said unsaturated compound can be used individually by 1 type or in mixture of 2 or more types.

  [A] The lower limit of the content of the structural unit (I) with respect to all the structural units of the polymer is preferably 5% by mass, more preferably 10% by mass, and even more preferably 15% by mass. By setting the content of the structural unit (I) to be equal to or higher than the above lower limit, the stability of the multiple exposure portion can be further increased. On the other hand, as this upper limit, 50 mass% is preferable and 40 mass% is more preferable. By setting the content of the structural unit (I) to be equal to or lower than the above upper limit, the low residue property and the like can be improved. In addition, content of each structural unit in a polymer can be considered that it is the same as the preparation ratio (mass ratio) of the unsaturated compound which gave each structural unit used in the case of superposition | polymerization (hereinafter the same).

(Structural unit (II))
The structural unit (II) is a structural unit represented by the following formula (3). The structural unit (II) may be composed of only one type of structural unit, or may be composed of a plurality of types of structural units.

In formula (3), R ^A represents a hydrogen atom or a methyl group. X is a C5-C30 alicyclic hydrocarbon group, a phenyl group, or a benzyl group.

R ^A is a hydrogen atom or a methyl group, and is preferably a methyl group.

  The alicyclic hydrocarbon group having 5 to 30 carbon atoms represented by X is as described above.

  The upper limit of the carbon number of X is 30, but 20 is preferable, 16 is more preferable, 12 is more preferable, and 10 is more preferable. Moreover, although the minimum of the carbon number of said X is 5, 6 may be sufficient. By making the carbon number of X not more than the above upper limit, the hydrophobicity becomes more appropriate, and the resolution, low residue property and the like can be particularly improved. On the other hand, by setting the number of carbon atoms of X to be equal to or more than the above lower limit, hydrophobicity can be increased, and stability of multiple exposure parts, development adhesion, and the like can be improved. When X is an alicyclic hydrocarbon group having 5 to 30 carbon atoms, the upper limit of the number of ring members (carbon number) of the alicyclic structure of the alicyclic hydrocarbon group is 30, but 20 is preferable. 16 is more preferable, 12 is more preferable, and 10 is still more preferable. On the other hand, the lower limit of the number of ring members is preferably 5, and more preferably 6.

  As said X, an alicyclic hydrocarbon group is preferable and a saturated alicyclic hydrocarbon group is more preferable.

Examples of the unsaturated compound that gives the structural unit (II) include cyclopentyl acrylate, cyclohexyl acrylate, cyclooctyl acrylate, cyclohexenyl acrylate, norbornyl acrylate, dicyclopentanyl acrylate, isobornyl acrylate, and tricyclo [5.2. 1.0 ^2,6 ] Acrylic acid cyclic alkyl ester such as decan-8-yl acrylate;
Cyclopentyl methacrylate, cyclohexyl methacrylate, cyclooctyl methacrylate, cyclohexenyl methacrylate, norbornyl methacrylate, dicyclopentanyl methacrylate, isobornyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, etc. A cyclic alkyl ester of methacrylic acid;
Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate;
Examples thereof include methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate. The said unsaturated compound can be used individually by 1 type or in mixture of 2 or more types.

  [A] The lower limit of the content of the structural unit (II) with respect to all the structural units of the polymer is preferably 10% by mass, more preferably 20% by mass, further preferably 30% by mass, and may be 40% by mass. . On the other hand, as this upper limit, 70 mass% is preferable, 60 mass% is more preferable, and 50 mass% may be sufficient. By making content of structural unit (II) more than the said minimum, hydrophobicity can be improved and multiple exposure part stability, image development adhesiveness, etc. can be improved. On the other hand, when the content of the structural unit (II) is not more than the above upper limit, good resolution, low residue properties, and the like can be exhibited.

(Structural unit (III))
[A] The polymer preferably further has a structural unit (III) having a carboxy group as a structural unit other than the structural unit (I) and the structural unit (II). [A] When the polymer has the structural unit (III), good low-residue properties with respect to an alkali developer can be exhibited.

Examples of the unsaturated compound that gives the structural unit (III) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and 4-vinylbenzoic acid;
Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;
The anhydride of the said unsaturated dicarboxylic acid etc. are mentioned. The said unsaturated compound can be used individually by 1 type or in mixture of 2 or more types.

  [A] The lower limit of the content of the structural unit (III) with respect to all the structural units of the polymer is preferably 1% by mass, more preferably 5% by mass, and may be 10% by mass. On the other hand, as this upper limit, 40 mass% is preferable, 30 mass% is more preferable, 25 mass% is further more preferable, and 20 mass% may be sufficient. By setting the content of the structural unit (III) to the above lower limit or more, sensitivity, low residue property, and the like can be further improved. Conversely, by setting the content to be equal to or less than the above upper limit, a sufficient amount of the structural unit (I) can be contained, and therefore, the multiple exposure portion stability and the development adhesion can be further improved.

(Structural unit (IV))
[A] The polymer may further have a structural unit (IV) derived from a hydrolyzable silane compound having an unsaturated double bond as a structural unit other than the structural units (I) to (III). Good. [A] When the polymer has the structural unit (IV), sensitivity, resolution, multiple exposure portion stability, and the like can be further improved. As the structural unit (IV), a structural unit having an alkoxysilyl group is preferable, and a structural unit having a trialkoxysilyl group is more preferable.

Examples of the hydrolyzable silane compound having an unsaturated double bond include 3- (trimethoxysilyl) propyl methacrylate, 3- (triethoxysilyl) propyl methacrylate, N-3- (methacryloxy-2-hydroxypropyl) -3. -Aminopropyltriethoxysilane, 2- (trimethoxysilyl) ethyl methacrylate, 2- (triethoxysilyl) ethyl methacrylate, trimethoxysilylmethyl methacrylate, methacryloxypropyltris (methoxyethoxy) silane, triethoxysilylmethyl methacrylate, 3 -[Tris (trimethylsiloxy) silyl] propyl methacrylate, 3- [Tris (dimethylvinylsiloxy)] propyl methacrylate, 3- (trimethoxysilyl) propyl acrylate, 3- (toluene) Etc. triethoxysilyl) propyl acrylate, having a trialkoxysilyl group (meth) can be mentioned acrylic acid esters. These compounds can be used individually by 1 type or in mixture of 2 or more types.

  [A] The lower limit of the content of the structural unit (IV) with respect to all the structural units of the polymer is preferably 5% by mass, more preferably 10% by mass, and more preferably 20% by mass. On the other hand, as this upper limit, 70 mass% is preferable and 50 mass% is more preferable. By making content of structural unit (IV) into the said range, a sensitivity, resolution, multiple exposure part stability, etc. can be improved more.

(Structural unit (V))
[A] The polymer may further have a structural unit (V) other than the structural units (I) to (IV).

Examples of the unsaturated compound that gives the structural unit (V) include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, and isodecyl methacrylate. Methacrylic acid chain alkyl esters such as n-lauryl methacrylate, tridecyl methacrylate and n-stearyl methacrylate;
Methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, n-lauryl acrylate, tridecyl acrylate, n-acrylate Acrylic acid chain alkyl esters such as stearyl;
Unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
unsaturated aromatic compounds such as m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene;
Conjugated dienes such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene;
Unsaturated compounds containing a tetrahydrofuran skeleton such as tetrahydrofurfuryl methacrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one;
Other examples include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate. The said unsaturated compound can be used individually by 1 type or in mixture of 2 or more types.

  [A] The lower limit of the content of the structural unit (V) with respect to all the structural units of the polymer is not particularly limited, but is preferably 1% by mass and more preferably 3% by mass. On the other hand, the upper limit may be, for example, 70% by mass, but is preferably 30% by mass, more preferably 10% by mass, and further preferably 5% by mass. By setting the content of the structural unit (V) within the above range, the multiple exposure portion stability, the development adhesiveness, and the like are more satisfactorily exhibited.

  [A] The lower limit of the weight average molecular weight (Mw) in terms of polystyrene by GPC of the polymer is preferably 5,000, and more preferably 10,000. On the other hand, the upper limit is preferably 30,000, and more preferably 20,000. By making Mw more than the said lower limit, the film formability of the said radiation sensitive resin composition can be made favorable. On the other hand, by making Mw equal to or less than the above upper limit value, the low residue property of the radiation-sensitive resin composition and the like are more favorably exhibited.

  As a minimum of the content rate of [A] polymer in the total solid in the said radiation sensitive resin composition, it can be set as 50 mass%, for example, and 55 mass% is preferable. On the other hand, as this upper limit, it can be 80 mass%, for example, and 70 mass% is preferable. [A] By making content of a polymer into the said range, the suppression capability of exposure nonuniformity, low residue property, etc. are exhibited more favorably.

  [A] A polymer is obtained by radical polymerization in the presence of an appropriate solvent, radical polymerization initiator, chain transfer agent, etc., using an unsaturated compound (compound having a radical polymerizable group) that gives each structural unit. be able to.

<[B] generating agent>
[B] The generator (at least one selected from a photoacid generator and a photobase generator) functions as an initiator for ionic polymerization (cationic polymerization or anionic polymerization). In the radiation-sensitive resin composition, since the [B] generator is contained, the [A] compound and the like are ion-polymerized and cured by irradiation of radiation (visible light, ultraviolet light, far ultraviolet light, etc.), and uneven exposure is caused. A cured film (interlayer insulating film or the like) that is small and excellent in stability of the multiple exposure portion can be formed. [B] The generator may be used alone or in combination of two or more.

  [B] Examples of the generator include a photoacid generator (radiation-sensitive cationic polymerization initiator) and a photobase generator (radiation-sensitive anionic polymerization initiator), and a photoacid generator is preferred.

  [B] The generator includes ionic compounds and nonionic compounds, but nonionic compounds are preferred. By using a nonionic generator, the light transmittance of the obtained cured film can be increased.

(Photoacid generator)
The photoacid generator refers to a compound that generates an acid upon irradiation with light or other radiation. Examples of radiation include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams. By using the photoacid generator, in the radiation sensitive resin composition, cationic polymerization of the [A] polymer usually occurs upon irradiation with radiation. Examples of the photoacid generator include oxime sulfonate compounds, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, onium salts and the like. Among these, oxime sulfonate compounds, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylic acid ester compounds are nonionic compounds. On the other hand, onium salts are ionic compounds.

(Oxime sulfonate compound)
As said oxime sulfonate compound, the compound containing the oxime sulfonate group represented by following formula (4) is preferable.

In Formula (4), R ^B1 is an alkyl group, a cycloalkyl group, or an aryl group, and part or all of the hydrogen atoms of these groups may be substituted with a substituent.

The alkyl group for R ^B1 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R ^B1 includes an alkoxy group having 1 to 10 carbon atoms or an alicyclic group (including a bridged alicyclic group such as a 7,7-dimethyl-2-oxonorbornyl group, preferably bicycloalkyl. Group) and the like. As the aryl group for R ^B1, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group and a naphthyl group are more preferable. The aryl group of R ^B1 may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group, or a halogen atom.

  The compound containing an oxime sulfonate group represented by the above formula (4) is more preferably an oxime sulfonate compound represented by the following formula (5).

In Formula (5), R ^B1 has the same ^{meaning as} the description of R ^B1 in Formula (4). X is an alkyl group, an alkoxy group, or a halogen atom. m is an integer of 0-3. When m is 2 or 3, the plurality of X may be the same or different. The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

  The alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom as X is preferably a chlorine atom or a fluorine atom. m is preferably 0 or 1. In particular, in the formula (5), a compound in which m is 1, X is a methyl group, and the substitution position of X is ortho is preferable.

  Specific examples of the oxime sulfonate compound include, for example, compound (5-i) [(5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], compound (5-ii) [(5H-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], compound (5-iii) [(camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-( 2-methylphenyl) acetonitrile], compound (5-iv) [(5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile] and compound (5-v) [ (5-octylsulfonyloxyimino)-(4-methoxy Phenyl) acetonitrile], and the like.

  These can be used alone or in combination of two or more, and can also be used in combination with other [B] generators. Compound (5-i) [(5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], compound (5-ii) [(5H-octylsulfonyloxyimino-5H -Thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], compound (5-iii) [(camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], compound ( 5-iv) [(5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile] and compound (5-v) [(5-octylsulfonyloxyimino)-( 4-methoxyphenyl) acetonitrile] is available as a commercial product Come.

(Sulfonimide compound)
Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) -1,8-naphthalenedicarboimide, N- (camphorsulfonyloxy) naphthyl dicarboxyimide, and the like. The sulfonimide compounds described in JP-A-2015-194583 and JP-A-2006-206503 can also be used as the photoacid generator.

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

(Diazomethane compound)
Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane and bis (cyclohexylsulfonyl) diazomethane. Diazomethane compounds described in JP-A-2015-18131 and JP-A-2006-87486 can also be used as a photoacid generator.

(Sulfone compound)
Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds, diaryldisulfone compounds, and the like.

(Sulfonate compound)
Examples of the sulfonic acid ester compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates.

(Carboxylic acid ester compound)
Examples of the carboxylic acid ester compound include carboxylic acid o-nitrobenzyl ester.

(Onium salt)
Examples of the onium salt include diphenyliodonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, and tetrahydrothiophenium salt.

  Examples of the diphenyl iodonium salt include diphenyl iodonium tetrafluoroborate and diphenyl iodonium hexafluorophosphonate. Diphenyliodonium salts described in JP2014-174235A and JP2016-87486A can also be used as the photoacid generator.

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

  Examples of the sulfonium salt include alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts, substituted benzylsulfonium salts and the like.

  Examples of the alkylsulfonium salt include 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate and 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate. Alkylsulfonium salts described in JP2014-157252A and JP2016-87486A can also be used as the photoacid generator.

  Examples of the benzylsulfonium salt include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate and benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate. Benzylsulfonium salts described in JP2015-18131A, JP2016-87486A, and the like can also be used as a photoacid generator.

  Examples of the dibenzylsulfonium salt include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate and dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate. Dibenzylsulfonium salts described in JP-A-2015-18131 and JP-A-2006-87486 can also be used as a photoacid generator.

  Examples of the substituted benzylsulfonium salt include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate and p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate. Substituted benzylsulfonium salts described in JP2014-157252A and JP2016-87486A can also be used as a photoacid generator.

  Examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, and 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-butoxynaphthyltetrahydrothiophenium trifluoromethanesulfonate, 4,7-di-n-butoxynaphthyltetrahydrothiophenium-10-camphorsulfonate, and the like. Can be mentioned. Tetrahydrothiophenium salts described in JP2014-157252A and JP2016-87486A can also be used as a photoacid generator.

  Among these photoacid generators, nonionic photoacid generators are preferred, and oxime sulfonate compounds and sulfonimide compounds are more preferred.

(Photobase generator)
A photobase generator refers to a compound that generates a base upon irradiation with light or other radiation. By using a photobase generator, anion polymerization of the [A] compound usually occurs in the radiation-sensitive resin composition by irradiation with radiation. Examples of the photobase generator include heterocyclic group-containing photobase generators such as N- (2-nitrobenzyloxycarbonyl) pyrrolidine and 1- (anthraquinone-2-yl) ethylimidazolecarboxylate;
2-nitrobenzyl cyclohexyl carbamate, etc. can be mentioned. Base generators such as heterocyclic group-containing photobase generators described in JP-A-2006-121311 and JP-A-2006-184117 can also be used as the base generator in the radiation-sensitive resin composition.

  Among the photobase generators, nonionic photobase generators are preferred, and heterocyclic group-containing photobase generators are more preferred from the standpoint that pattern resolution can be further improved.

  [B] The lower limit of the content of the generator is preferably 1 part by mass and more preferably 3 parts by mass with respect to 100 parts by mass of the polymer [A]. On the other hand, as this upper limit, 20 mass parts is preferable and 10 mass parts is more preferable. [B] By making the content rate of a generator into the said range, favorable multiple exposure part stability, sclerosis | hardenability, etc. can be exhibited.

<[B] Radiation sensitive radical polymerization initiator>
The radiation sensitive resin composition may use [b] a radiation sensitive radical polymerization initiator together with the [B] generator. [B] As the radiation-sensitive radical polymerization initiator, a known one such as an O-acyl oxime compound can be used.

  When the said radiation sensitive resin composition contains [b] a radiation sensitive radical polymerization initiator, as content of this [b] radiation sensitive radical polymerization initiator, for example, [A] 100 mass parts of polymers To 1 part by mass or more and 30 parts by mass or less.

<[C] Compound>
The compound [C] is a compound having a molecular weight of 2000 or less having one or more polymerizable groups in one molecule. By including the [C] compound in the museum radiation resin composition, the sensitivity, resolution, low residue, development adhesion, multiple exposure part stability, and the like can be further improved. [C] The compound preferably has a plurality of polymerizable groups.

  Examples of the polymerizable group include a cyclic ether group, a (meth) acryloyl group, a formyl group, an acetyl group, a vinyl group, an isopropenyl group, and an alkoxymethylated amino group. Among these, as the polymerizable group, a cyclic ether group, a (meth) acryloyl group, and an alkoxymethylated amino group are preferable, a cyclic ether group and a (meth) acryloyl group are more preferable, and a cyclic ether group is more preferable. . In the case of having such a polymerizable group, in addition to the stability of the multiple exposure part, it is possible to further improve the development adhesiveness and the like. As the cyclic ether group, an oxiranyl group, a 3,4-epoxycyclohexyl group, and an oxetanyl group are preferable. These cyclic ether groups may be those in which some or all of the hydrogen atoms are substituted with a substituent such as an alkyl group.

  Examples of the compound having a plurality of oxiranyl groups include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD dihydrogen. Polyglycidyl ethers of bisphenol such as glycidyl ether; 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene Polyglycidyl ethers of polyhydric alcohols such as glycol diglycidyl ether; ethylene glycol, propylene Aliphatic polyglycidyl ethers of polyether polyols obtained by adding one or two or more alkylene oxides to aliphatic polyhydric alcohols such as glycol and glycerin; A compound having an epoxycyclohexyl group; a phenol novolac epoxy resin such as a bisphenol A novolac epoxy resin; a cresol novolac epoxy resin; a polyphenol epoxy resin; a cyclic aliphatic epoxy resin; a diglycidyl ester of an aliphatic long-chain dibasic acid; Glycidyl esters of higher fatty acids; epoxidized soybean oil, epoxidized linseed oil and the like.

  As a commercial product of a compound having a plurality of oxiranyl groups, for example, as bisphenol A type epoxy resin, Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828 (manufactured by Japan Epoxy Resin Co., Ltd.) ); As bisphenol F type epoxy resin, Epicoat 807 (manufactured by Japan Epoxy Resin Co., Ltd.); As phenol novolac type epoxy resin (bisphenol A novolac type epoxy resin, etc.) EPPN201, 202 (made by Nippon Kayaku Co., Ltd.); EOCN102, 103S, 104S, 1020, 1025, 1027 (made by Nippon Kayaku Co., Ltd.), Epicoat 180S7 as a cresol novolac type epoxy resin (Manufactured by Japan Epoxy Resin Co., Ltd.); EP1032H60, XY-4000 (manufactured by Japan Epoxy Resin Co.) as polyphenol type epoxy resins; CY-175, 177, 179, Araldite CY-182 as cyclic aliphatic epoxy resins, 192, 184 (Ciba Specialty Chemicals), ERL-4234, 4299, 4221, 4206 (UCC), Shodyne 509 (Showa Denko), Epicron 200, 400 (Manufactured by DIC), Epicoat 871, 872 (manufactured by Japan Epoxy Resin), ED-5661, 5562 (manufactured by Celanese Coating); TMP (manufactured by NOF Corporation) etc. It is possible.

  Examples of the compound having a plurality of 3,4-epoxycyclohexyl groups include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro. -3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methyl Cyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylene Screw 3,4-epoxycyclohexane carboxylate), lactone-modified 3,4-epoxycyclohexylmethyl-3 ', may be mentioned 4'-epoxycyclohexane carboxylate.

  As a compound having a plurality of oxetanyl groups, for example, commercially available products such as OXT-121, OXT-221, OXT-191, OX-SQ-H, PNOX-1009, RSOX (manufactured by Toagosei Co., Ltd.), etanacol OXBP, etanacol OXTP ( Ube Industries, Ltd.).

  Examples of the compound having a plurality of (meth) acryloyl groups include bifunctional (meth) acrylic acid esters and trifunctional or higher functional (meth) acrylic acid esters.

  Examples of the bifunctional (meth) acrylic acid ester include ethylene glycol di (meth) acrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetra Examples include ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, tricyclodecane methanol diacrylate, and the like. It is done.

  Examples of the trifunctional or higher functional (meth) acrylic acid ester include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetra Methacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, Li (2-acryloyloxyethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate, succinic acid modified pentaerythritol triacrylate, side chain acryloyl group bis F resin, succinic acid modified dipentaerythritol pentaacrylate, A compound having a chain alkylene group and an alicyclic structure and having two or more isocyanate groups, and one or more hydroxy groups in the molecule, and 3, 4, or 5 (meta And polyfunctional urethane acrylate compounds obtained by reacting with a compound having an acryloyloxy group.

  Examples of compounds having an alkoxymethylated amino group include melamine compounds such as hexamethoxymethyl melamine and hexabutoxymethyl melamine, and glycoluril compounds such as tetramethoxymethyl glycoluril and tetrabutoxyglycoluril.

  [C] The lower limit of the content of the compound with respect to 100 parts by mass of the [A] polymer is preferably 10 parts by mass, more preferably 20 parts by mass, and even more preferably 30 parts by mass. On the other hand, the upper limit of this content is preferably 100 parts by mass, and more preferably 70 parts by mass. In the radiation sensitive resin composition, it is preferable that the content of the [C] compound is relatively reduced with respect to the [A] polymer. In this case, even when the [C] compound is polymerized and cured, the shrinkage of the film accompanying the polymerization can be suppressed, and the difference in shrinkage between the normal exposure portion and the multiple exposure portion can be reduced. By setting the content of the [C] compound to the above lower limit or more, sensitivity, resolution, development adhesion, and the like can be improved. On the other hand, by making the content of the [C] compound not more than the above upper limit, the occurrence of exposure unevenness can be effectively reduced.

<[D] Colorant>
The radiation sensitive resin composition may contain a colorant [D] for the purpose of coloring the resulting cured film. [D] Examples of the colorant include pigments and dyes.

(Pigment)
The pigment may be either an organic pigment or an inorganic pigment, and examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists). Specifically, those having the following color index (CI) names are mentioned.

C. I. Pigment Yellow 12, 13 and 14;
C. I. Pigment orange 5, 13, 13, 38;
C. I. Pigment Red 1, 2 and 5;
C. I. Pigment violet 1, 19 and 23;
C. I. Pigment Blue 15, 15: 3, 15: 4;
C. I. Pigment Green 7, 36, 58;
C. I. Pigment Brown 23 and 25;
C. I. Pigment Black 1, 7 etc.

  Examples of the inorganic pigment include titanium oxide, barium sulfate, titanium black, synthetic iron black, and carbon black. The pigments described in JP 2010-61041 A, JP 2012-63745 A, and the like can also be used as the pigment of the radiation sensitive resin composition.

(dye)
In the radiation sensitive resin composition, a dye may be contained as a colorant [D]. The radiation sensitive resin composition for forming a red pixel can contain a red dye as a [D] colorant. Similarly, the radiation sensitive resin composition for forming a green pixel and a blue pixel can contain a green dye and a blue dye, respectively, as the [D] colorant. Each of the red dye, the green dye, and the blue dye may be composed of one kind of dye, or may be composed of two or more kinds of dyes so as to have desired light absorption characteristics. For example, a radiation-sensitive resin composition for forming a green pixel is often composed of a combination of a cyan dye and a yellow dye because desired light absorption characteristics can be easily obtained.

  Preferred dyes have a high extinction coefficient, desired light absorption characteristics (particularly low side absorption), excellent compatibility with other components (particularly [A] polymer), and [H] described later. It is selected from those excellent in solubility in a solvent. Such dyes include phthalocyanine dyes, methine dyes, azo dyes, pyromethene dyes, xanthene dyes, and triarylmethane dyes. The dyes described in JP2011-178865A, JP2013-92784A, JP2014-35497A, JP2015-68852A, and the like can also be used as the [D] colorant.

  [D] As a minimum of content of a coloring agent, 1 mass part is preferred to 100 mass parts of [A] polymer in conversion of solid content, 5 mass parts is more preferred, and 10 mass parts is still more preferred. On the other hand, as this upper limit, 80 mass parts is preferable, 50 mass parts is more preferable, and 30 mass parts is further more preferable.

<[E] Adhesion aid>
The radiation sensitive resin composition preferably further contains [E] an adhesion assistant. [E] The adhesion assistant is a component that improves the adhesion between the obtained cured film and the substrate. [E] As the adhesion assistant, a silane coupling agent having a reactive functional group such as a carboxy group, a methacryloyl group, a vinyl group, an isocyanate group, an epoxy group, or an amino group is preferable.

  Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, methyldimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxyethyltrimethoxysilane, N -(2-aminoethyl) 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, etc. be able to.

  Commercially available products of these functional silane coupling agents include, for example, Silaace S210, S220, S310, S320, S330, S510, S520, S530, S710 (above, manufactured by Chisso Corporation), A-151, A-171, A- 172, A-174, Y-9936, A-186, A-187, A-1100, A-1110, A-1120, A-1122, Y-9669, A-1160 (manufactured by Nihon Unicar), SH6020, SZ6023, SH6026, SZ6030, SZ6032, SH6040, SZ6050, SZ6070, SZ6072, SZ6075, SZ6083, SZ6300, XIAMETER (R) OFS-6030 SILANE (above, manufactured by Toray Dow Corning Silicone) . Silane coupling agents described in JP 2003-288991 A, JP 2010-8603 A, and the like can also be used as the silane coupling agent of the radiation-sensitive resin composition.

  [E] The lower limit of the content of the adhesion assistant is preferably 0.1 parts by mass, more preferably 1 part by mass, and still more preferably 3 parts by mass with respect to 100 parts by mass of the polymer [A]. On the other hand, as this upper limit, 20 mass parts is preferable, 10 mass parts is more preferable, and 7 mass parts is further more preferable.

<[F] Polymerization inhibitor>
The said radiation sensitive resin composition can contain a [F] polymerization inhibitor. [F] The polymerization inhibitor can improve the storage stability of the radiation-sensitive resin composition. [F] Examples of the polymerization inhibitor include sulfur, quinones, hydroquinones, polyoxy compounds, amines, nitronitroso compounds, and more specifically, p-methoxyphenol, 2,5-di-t- Examples thereof include butylhydroquinone and N-nitroso-N-phenylhydroxylamine aluminum.

  As an upper limit of content of the [F] polymerization inhibitor in the said radiation sensitive resin composition, 1 mass part is preferable with respect to 100 mass parts of [A] polymers, and 0.3 mass part is more preferable. [F] When the content of the polymerization inhibitor exceeds the above upper limit, the sensitivity of the radiation-sensitive resin composition may be reduced, and the pattern shape may be deteriorated. In addition, the minimum of content of this [F] polymerization inhibitor can be 0.01 mass part, for example.

<[G] Surfactant>
The radiation sensitive resin composition preferably further contains a [G] surfactant. When the said radiation sensitive resin composition contains [G] surfactant, since wettability to the board | substrate etc. which form a coating film can be improved, applicability | paintability improves. In addition, [G] surfactant may be used independently and may be used in combination of 2 or more type.

  [G] As the surfactant, a fluorine-based surfactant and a silicone-based surfactant are preferable, and a silicone-based surfactant is more preferable.

[G] Examples of commercially available surfactants include Polyflow KL-401, KL-402, KL-403, and KL-404 (all manufactured by Kyoeisha);
BYK-302, BYK-307, BYK-325, BYK-331, BYK-333, BYK348, BYK378, BYK-UV-3535, BYK-UV-3530, BYK-UV-3500, BYK-381, BYK-3441 ( Above, manufactured by Big Chemie Japan)
DAW CORNING TORAY 8019 ADDITIVE, DOW CORNING TORAY 1313 ANTIFORM EMULSION (manufactured by Toray Dow Corning).

  Content of the [G] surfactant in the said radiation sensitive resin composition can be 0.01 mass part or more and 1 mass part or less with respect to 100 mass parts of [A] polymers, for example.

<[H] solvent>
The radiation-sensitive resin composition preferably further contains a [H] solvent. [H] As the solvent, a solvent that uniformly dissolves or disperses the other components contained in the radiation-sensitive resin composition and does not react with the components is used.

[H] As the solvent, for example, alcohols such as methanol, ethanol, isopropyl alcohol, butanol and octanol;
Esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate;
Ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene diglycol monomethyl ether, ethylene diglycol ethyl methyl ether;
Amides such as dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; Aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene be able to.

  [H] As the solvent, esters are preferred. [H] The solvent may be used alone or in combination of two or more.

<Other ingredients>
The said radiation sensitive resin composition can further contain other components other than the [A]-[H] component and the [b] component which were mentioned above. Examples of such other components include antioxidants, chain transfer agents, fillers, and polymers other than the [A] polymer. The said radiation sensitive resin composition may use said each component individually or in combination of 2 or more types. In addition, as an upper limit of content of other components other than said [A]-[H] component and [b] component, it may be 20 mass%, for example, may be 5 mass%, and may be 1 mass. %.

<Method for preparing radiation-sensitive resin composition>
In the radiation-sensitive resin composition, the [A] polymer, the [B] generator, and other components as necessary are mixed in a predetermined ratio, and preferably dissolved or dispersed in an appropriate [H] solvent. Can be prepared. The prepared radiation-sensitive resin composition is preferably filtered through, for example, a filter having a pore diameter of about 0.2 μm. As solid content concentration of the said radiation sensitive resin composition, it is 10 to 50 mass%, for example. In the case where the radiation-sensitive resin composition contains a pigment as the colorant [D], first, after preparing a pigment dispersion containing the pigment, by mixing the pigment dispersion with other components, The radiation sensitive resin composition can be prepared.

<Method for producing cured film for display element>
A method for producing a cured film for a display element (hereinafter also simply referred to as “cured film”) according to an embodiment of the present invention includes:
(1) A step of forming a coating film on a substrate using the radiation sensitive resin composition (hereinafter, also referred to as “step (1)”),
(2) a step of multiple exposure of at least a part of the coating film (hereinafter also referred to as “step (2)”); and (3) a step of developing the coating film (hereinafter also referred to as “step (3)”). ).

The production method preferably further comprises (4) a step of heating the coating film (hereinafter also referred to as “step (4)”) after development.

  The manufacturing method of the display element cured film can be effectively performed by using a scanning exposure apparatus for exposure. In this case, high-speed exposure of a large substrate becomes possible, and productivity of display elements such as a flat panel display can be increased. In addition, since the radiation sensitive resin composition has the above-mentioned properties, at least a part of the region on the substrate is subjected to multiple exposure, and when a pattern or the like is formed in the region, exposure at the multiple exposure part is performed. Unevenness can be reduced. The multiple exposure portion may be, for example, a double exposure portion or triple exposure or more. Hereinafter, each process is explained in full detail.

[Step (1)]
In this step, a coating film is formed on the substrate using the radiation-sensitive resin composition. Specifically, the radiation-sensitive resin composition in the form of a solution is applied to the substrate surface, and preferably a prebake is performed to remove the solvent and form a coating film. Examples of the substrate include a glass substrate, a silicon substrate, a plastic substrate, and a substrate on which various metal thin films are formed. Examples of the plastic substrate include a resin substrate made of plastic such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethersulfone, polycarbonate, polyimide, and the like.

As a coating method, for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an ink jet method can be employed. Of these, spin coating, bar coating, and slit die coating are preferred as the coating method. The pre-baking conditions vary depending on the type of each component, the use ratio, and the like, but can be, for example, 60 ° C. or higher and 130 ° C. or lower and 30 seconds or longer and 10 minutes or shorter. The film thickness of the coating film to be formed is preferably 0.1 μm or more and 8 μm or less as a value after pre-baking.

[Step (2)]
In this step, a part of the coating film is irradiated with radiation. Specifically, the coating film formed in step (1) is irradiated with radiation through a mask having a predetermined pattern. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams. At this time, a part of the coating film is irradiated with radiation twice or more. That is, in this step, a part of the coating film is subjected to multiple exposure.

Examples of the ultraviolet rays include g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), and the like. Examples of the far ultraviolet light include KrF excimer laser light. Examples of X-rays include synchrotron radiation. Examples of the charged particle beam include an electron beam. Among these radiations, ultraviolet rays are preferable, and among the ultraviolet rays, radiation containing g-line, h-line and / or i-line is more preferable. The exposure dose of radiation is preferably 0.1 J / m ² or more and 20,000 J / m ² or less.

  In this step, a scanning exposure apparatus is preferably used as the radiation irradiation apparatus. The scanning exposure apparatus is configured to irradiate a plurality of irradiated regions on a photomask and project images of the plurality of irradiated regions onto a coating film on a substrate via the plurality of projection optical systems. .

[Step (3)]
In this step, the coating film irradiated with the radiation is developed. In the production method, negative development is usually performed. Specifically, the coating film irradiated with radiation in the step (2) is developed with a developing solution to remove the non-irradiated part of the radiation. Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyl Diethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo Examples thereof include an aqueous solution of an alkali (basic compound) such as [4,3,0] -5-nonane. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous alkali solution, or an alkaline aqueous solution containing a small amount of various organic solvents capable of dissolving the radiation-sensitive resin composition is used as a developer. It may be used as

  As a developing method, for example, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, or a shower method can be employed. The development time varies depending on the composition of the radiation sensitive resin composition, but can be, for example, 30 seconds or longer and 120 seconds or shorter. In addition, it is preferable to perform the rinse process etc. by running water washing | cleaning with respect to the patterned coating film after a image development process.

[Step (4)]
In this step, the developed coating film is heated. Although it does not specifically limit as a heating method, For example, it can heat using heating apparatuses, such as oven and a hotplate. As heating temperature in this process, it can be set as 120 to 250 degreeC, for example. The heating time varies depending on the type of heating equipment, but for example, when heat treatment is performed on a hot plate, it is 5 minutes to 40 minutes, and when heat treatment is performed in an oven, it is 30 minutes to 80 minutes. be able to. In this way, a desired patterned cured film can be formed on the substrate.

  According to the said manufacturing method, the cured film for display elements with which the exposure nonuniformity resulting from multiple exposure was reduced can be obtained. The manufacturing method also has good resolution. Furthermore, in the production method, by adjusting the composition of the radiation sensitive resin composition, the sensitivity, low residue property and development adhesion can be improved, and a cured film having good hardness, resolution, adhesion and the like can be obtained. .

<Curing film for display element>
The cured film for display elements which concerns on one Embodiment of this invention is a hardened | cured material of the said radiation sensitive resin composition. Since the cured film for display elements is formed from the radiation-sensitive resin composition, the unevenness in exposure is small and the film thickness is uniform. Further, the cured film for display element also has various properties such as hardness and adhesion. In particular, the cured film for display element can be suitably applied to a display element having a large screen. The said display element cured film can be suitably manufactured with the manufacturing method of the display element cured film mentioned above. The cured film for display element is used as an interlayer insulating film, a color filter, a spacer, or the like, and among these, it is preferable to be used as an interlayer insulating film.

<Display element>
The display element which concerns on one Embodiment of this invention is equipped with the said cured film for display elements. Examples of the display element include a liquid crystal display element and a plasma display. Since the display element includes the cured film for display element, the display element is excellent in general characteristics required for practical use.

  In the liquid crystal display element which is an example of the display element, for example, two TFT array substrates having a liquid crystal alignment film formed on the surface are arranged on the liquid crystal alignment film side through a sealant provided in the peripheral portion of the TFT array substrate. The liquid crystal is filled between these two TFT array substrates. The TFT array substrate has wirings arranged in layers, and the wirings are insulated by the cured film for display elements as an interlayer insulating film.

<Other embodiments>
The present invention is not limited to the embodiment described above. For example, the radiation sensitive resin composition can be suitably used in a manufacturing method using an exposure apparatus other than the scanning exposure apparatus.

  EXAMPLES Hereinafter, although this invention is explained in full detail based on an Example, this invention is not interpreted limitedly to this Example. In addition, the characteristic of the copolymer obtained by a synthesis example was measured with the following method.

[Weight average molecular weight (Mw), number average molecular weight (Mn) and dispersity (Mw / Mn)]
Mw and Mn of the polymer were measured by gel permeation chromatography (GPC) under the following analytical conditions using Tosoh GPC columns (2 G2000HXL, 1 G3000HXL, 1 G4000HXL).
The degree of dispersion (Mw / Mn) was calculated from the measurement results of Mw and Mn.
(Analysis conditions)
Elution solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Column temperature: 40 ° C
Detector: Differential refractometer Standard material: Monodisperse polystyrene

[A] Monomers (unsaturated compounds) used for polymerization of the copolymers (A-1) to (A-10), which are polymers, are shown below.
A1-1: 3,4-epoxycyclohexylmethyl methacrylate (M-100)
A1-2: Glycidyl methacrylate (GMA)
A1-3: 3-ethyl-3-methacloyloxymethyloxetane (OXMA: (3-ethyloxetane-3-yl) methyl methacrylate)
A1-4: 2- (vinyloxyethoxy) ethyl methacrylate (“VEEM” from Nippon Shokubai Co., Ltd.)
A2-1: Cyclohexyl methacrylate (CHMA)
A2-2: Dicyclopentanyl methacrylate (Hitachi Chemical Co., Ltd. “FA-513MS”)
A2-3: Isobornyl acrylate ("IBXA" from Osaka Organic Chemical Industry Co., Ltd.)
A3: Methacrylic acid (MA)
A4: 3- (Triethoxysilyl) propyl acrylate (APTMS)
A5: Methyl methacrylate (MMA)

<[A] Synthesis of polymer>
[Synthesis Example 1] (Synthesis of copolymer (A-1))
A flask equipped with a condenser and a stirrer was charged with 5.1 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl 3-methoxypropionate. Subsequently, (A1-1) 3,4-epoxycyclohexylmethyl methacrylate 25 parts by mass, (A2-1) cyclohexyl methacrylate 55 parts by mass, (A3) methacrylic acid 16 parts by mass, (A5) methyl methacrylate 4 parts by mass, and After 0.5 parts by mass of α-methylstyrene dimer 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 the copolymer (A-1) (solid content concentration = 34.0% by mass, Mw = 14, 400, Mw / Mn = 2.2).

[Synthesis Example 2] (Synthesis of copolymer (A-2))
A flask equipped with a condenser and a stirrer was charged with 5.3 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl 3-methoxypropionate. Subsequently, (A1-2) glycidyl methacrylate 30 parts by mass, (A2-1) cyclohexyl methacrylate 54 parts by mass, (A3) methacrylic acid 16 parts by mass, and α-methylstyrene dimer 0.5 part by mass were charged with nitrogen. After that, 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 the copolymer (A-2) (solid content concentration = 33.3% by mass, Mw = 14, 000, Mw / M
n = 2.3).

[Synthesis Example 3] (Synthesis of copolymer (A-3))
A flask equipped with a condenser and a stirrer was charged with 5.1 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl 3-methoxypropionate. Subsequently, (A1-3) 3-ethyl-3-methacryloyloxymethyloxetane 30 parts by mass, (A2-1) cyclohexyl methacrylate 54 parts by mass, (A3) methacrylic acid 16 parts by mass, and α-methylstyrene dimer 0. After charging 5 parts by mass and substituting 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 the copolymer (A-3) (solid content concentration = 34.2% by mass, M
w = 14,700, Mw / Mn = 2.2).

[Synthesis Example 4] (Synthesis of copolymer (A-4))
A flask equipped with a condenser and a stirrer was charged with 7.4 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl 3-methoxypropionate. Subsequently, (A1-4) 2- (vinyloxyethoxy) ethyl methacrylate 25 parts by mass, (A2-1) cyclohexyl methacrylate 51 parts by mass, (A3) methacrylic acid 20 parts by mass, (A5) methyl methacrylate 4 parts by mass, And 0.5 mass part of (alpha) -methylstyrene dimer was prepared, and after nitrogen substitution, 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 the copolymer (A-4) (solid content concentration = 34.7% by mass, Mw = 17, 100, Mw / Mn = 2.5).

[Synthesis Example 5] (Synthesis of copolymer (A-5))
A flask equipped with a condenser and a stirrer was charged with 15.3 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl 3-methoxypropionate. Subsequently, (A1-1) 3,4-epoxycyclohexylmethyl methacrylate 20 parts by mass, (A2-1) cyclohexyl methacrylate 32 parts by mass, (A3) methacrylic acid 8 parts by mass, (A4) 3- (trimethoxysilyl) propyl After 40 parts by mass of acrylate and 0.5 part by mass of α-methylstyrene dimer 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 the copolymer (A-5) (solid content concentration = 32.5% by mass, Mw = 12, 100, Mw / Mn = 2.5).

[Synthesis Example 6] (Synthesis of copolymer (A-6))
A flask equipped with a condenser and a stirrer was charged with 15.3 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl 3-methoxypropionate. Subsequently, (A1-2) glycidyl methacrylate 20 parts by mass, (A2-1) cyclohexyl methacrylate 32 parts by mass, (A3) methacrylic acid 8 parts by mass, (A4) 3- (trimethoxysilyl) propyl acrylate 40 parts by mass, and After 0.5 parts by mass of α-methylstyrene dimer 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 the copolymer (A-6) (solid content concentration = 32.7% by mass, Mw = 11, 700, Mw / Mn = 2.6).

[Synthesis Example 7] (Synthesis of copolymer (A-7))
A flask equipped with a condenser and a stirrer was charged with 15.3 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl 3-methoxypropionate. Subsequently, (A1-3) 3-ethyl-3-methacryloyloxymethyloxetane 20 parts by mass, (A2-1) cyclohexyl methacrylate 32 parts by mass, (A3) methacrylic acid 8 parts by mass, (A4) 3- (trimethoxy After 40 parts by mass of silyl) propyl acrylate and 0.5 parts by mass of α-methylstyrene dimer 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 the copolymer (A-7) (solid content concentration = 33.4% by mass, Mw = 12, 000, Mw / Mn = 2.5).

[Synthesis Example 8] (Synthesis of copolymer (A-8))
A flask equipped with a condenser and a stirrer was charged with 7.2 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl 3-methoxypropionate. Subsequently, (A1-1) 3,4-epoxycyclohexylmethyl methacrylate 25 parts by mass, (A3) methacrylic acid 13 parts by mass, (A5) methyl methacrylate 62 parts by mass, and α-methylstyrene dimer 0.5 parts by mass. After charging and replacing 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 the copolymer (A-8) (solid content concentration = 34.1% by mass, Mw = 11, 500, Mw / Mn = 2.2).

[Synthesis Example 9] (Synthesis of copolymer (A-9))
A flask equipped with a condenser and a stirrer was charged with 8.5 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl 3-methoxypropionate. Subsequently, (A1-1) 3,4-epoxycyclohexylmethyl methacrylate 25 parts by mass, (A2-2) 57 parts by mass of dicyclopentanyl methacrylate, (A3) 18 parts by mass of methacrylic acid, and α-methylstyrene dimer 0 After charging 5 parts by mass and substituting 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 the copolymer (A-9) (solid content concentration = 32.9% by mass, Mw = 13, 300, Mw / Mn = 2.1).

[Synthesis Example 10] (Synthesis of copolymer (A-10))
A flask equipped with a condenser and a stirrer was charged with 15.3 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl 3-methoxypropionate. Subsequently, (A1-1) 3,4-epoxycyclohexylmethyl methacrylate 25 parts by mass, (A2-3) isobornyl acrylate 57 parts by mass, (A3) methacrylic acid 18 parts by mass, and α-methylstyrene dimer 0.5 Stirring was started gently after charging a mass part and replacing 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 copolymer (A-10) (solid content concentration = 34.0% by mass, Mw = 16, 500, Mw / Mn = 2.5).

  The mass ratio of each monomer in Synthesis Examples 1 to 10, and Mw and Mw / Mn of the obtained copolymer are shown in Table 1 again.

<[D] Preparation of pigment dispersion>
[Preparation Example 1] (Preparation of pigment dispersion (D-1))
15 parts by weight of C.I. I. Pigment Orange 38, 4 parts by mass of Ajisper PB822 (manufactured by Ajinomoto Fine Techno Co., Ltd.) as a dispersant, and 81 parts by mass of propylene glycol monomethyl ether acetate as a solvent were mixed and dispersed for 12 hours using a bead mill, D-1) was prepared.

<Preparation of radiation-sensitive resin composition>
[A] polymers, [B] generators, [C] compounds, [D] pigment dispersions, [E] adhesion assistants, [F] used in the preparation of the radiation-sensitive resin compositions of Examples and Comparative Examples The polymerization inhibitor, [G] surfactant and [H] solvent are shown below.

<[A] polymer>
A-1 to A-10: Copolymers synthesized in Synthesis Examples 1 to 10, respectively.

<[B] generating agent>
B-1: “NAI-105” of Midori Chemical Co., Ltd. (N- (trifluoromethylsulfonyloxy) -1,8-naphthalenedicarboimide represented by the following formula)

  B-2: “DBNS-T” of ADEKA (4,7-di-n-butoxynaphthyltetrahydrothiophenium trifluoromethanesulfonate represented by the following formula)

  B-3: “SP-231” of Midori Chemical Co., Ltd. (4,7-di-n-butoxynaphthyltetrahydrothiophenium-10-camphorsulfonate represented by the following formula)

  B-4: “IRGACURE PAG121” manufactured by BASF ((5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile represented by the following formula)

  B-5: “WPBG-140” manufactured by Wako Pure Chemical Industries, Ltd. (1- (anthraquinone-2-yl) ethylimidazolecarboxylate represented by the following formula)

b-1: “NCI-930” of ADEKA (O-acyloxime compound which is a radical polymerization initiator)
b-2: “IRGACURE OXE03” manufactured by BASF (O-acyloxime compound which is a radical polymerization initiator)

<[C] Compound>
C-1: “Aron Oxetane OXT-191” manufactured by Toagosei Co., Ltd. (compound represented by the following formula: where n is an average of 5)

  C-2: “EP1032H60” (compound represented by the following formula) manufactured by Japan Epoxy Resin Co., Ltd.

  C-3: Hexamethoxymethylmelamine (compound represented by the following formula)

  C-4: Nippon Kayaku's “KAYARAD DPHA” (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)

<[D] Pigment dispersion>
D-1: Pigment dispersion prepared in Preparation Example 1

<[E] Adhesion aid>
E-1: “Cyra Ace S510” from Chisso Corporation (functional silane coupling agent)
E-2: “XIAMETER® OFS-6030 SILANE” (functional silane coupling agent) manufactured by Toray Dow Corning

<[F] Polymerization inhibitor>
F-1: 2,5-di-t-butylhydroquinone

<[G] Surfactant>
G-1: “DOW CORNING TORAY 8019 ADDITIVE” by Toray Dow Corning

<[H] organic solvent>
G-1: Methyl 3-methoxypropionate G-2: Propylene glycol monomethyl ether acetate

<Example 1>
In the solution containing the copolymer (A-1), 5 parts by mass of the generator (B-1) and the compound (A) are added to the amount corresponding to 100 parts by mass (solid content) of the copolymer (A-1). C-1) 50 parts by mass, adhesion assistant (E-1) 5 parts by mass and surfactant (G-1) 0.15 parts by mass are mixed, and the solvent (so that the solid content concentration becomes 30% by mass. After dissolving in a mixed solvent of H-1) and solvent (H-2), the mixture was filtered through a membrane filter having a pore size of 0.2 μm to prepare a radiation sensitive resin composition of Example 1.

<Examples 2 to 22 and Comparative Example 1>
Except having used each component of the kind and compounding quantity (mass part) which are shown in following Table 2, it operates like Example 1 and each radiation sensitive resin composition of Examples 2-22 and Comparative Example 1 is used. Prepared. In Table 2, “-” indicates that the corresponding component was not blended.

<Evaluation>
For the radiation-sensitive resin compositions of Examples 1 to 22 and Comparative Example 1, sensitivity, resolution, low residue, development adhesion, transmittance (excluding Example 20), and multiple exposure were performed according to the methods described below. Partial stability was evaluated. The evaluation results are shown in Table 2.

[Sensitivity (Radiation sensitivity)]
After applying the radiation sensitive resin composition on a glass substrate using a spinner, it was pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 4.0 μm. Next, using an exposure machine (Canon's “MPA-600FA”: using an ultra-high pressure mercury lamp), the amount of exposure was changed, and the coating film was passed through a pattern mask having a plurality of rectangular light-shielding portions (10 μm × 10 μm). Exposure was performed. Next, a development process was performed at 25 ° C. by a liquid piling method using a tetramethylammonium hydroxide aqueous solution (developer) having a concentration of 2.38 mass%. The development processing time was 100 seconds. After the development treatment, the coating film was washed with running ultrapure water for 1 minute and dried to form a pattern on the glass substrate. This glass substrate was heated in a clean oven at 230 ° C. for 30 minutes to obtain a cured film. With respect to the film thickness of the cured film, the exposure amount at which the remaining film ratio (ratio in which the patterned thin film remains properly) represented by the following formula was 80% or more was obtained as sensitivity, and the sensitivity was evaluated according to the following criteria. The film thickness was measured by an optical interference type film thickness measuring device (“Lambda Ace VM-2210” manufactured by Screen).
Residual film ratio (%) = (film thickness after development / film thickness before development) × 100
(Evaluation criteria)
A: Less than 1000 J / m ² B: 1000 J / m ² or more and less than 5000 J / m ² C: 5000 J / m ² or more

[Resolution]
A cured film having a through hole was formed in the same manner as the evaluation of radiation sensitivity except that the exposure amount was 1000 J / m ^2, and the minimum diameter of the through hole of this cured film was observed with an optical microscope. The resolution was evaluated according to the following criteria.
(Evaluation criteria)
A: Minimum diameter of the through hole is 10 μm or more B: Minimum diameter of the through hole is 8 μm or more and less than 10 μm C: Minimum diameter of the through hole is 5 μm or more and less than 8 μm D: No through hole is formed

[Low residue]
A cured film having a through hole was formed in the same manner as in the evaluation of radiation sensitivity except that the exposure amount was 1000 J / m ^2, and the through hole of this cured film was observed with an optical microscope. The low residue property was evaluated according to the following criteria.
(Evaluation criteria)
A: A residue cannot be confirmed B: A residue can be confirmed slightly C: A residue can be confirmed clearly D: A residue can be confirmed in large quantities

[Development adhesion]
A cured film similar to the evaluation of the residue except that a mask having a line-and-space ratio (L / S) of 1: 1 (line width and space width is 20-5 μm) and the exposure amount is 1000 J / m ² Formed. About this cured film, the minimum width | variety of the line which remains without peeling after image development was observed with the optical microscope, and image development adhesiveness was evaluated according to the following references | standards.
(Evaluation criteria)
A: Minimum width is less than 10 μm B: Minimum width is not less than 10 μm and less than 30 μm C: Minimum width is not less than 30 μm D: All peeled

[Transmissivity (light transmittance)]
After applying the radiation sensitive resin composition on a glass substrate using a spinner, it was pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 4.0 μm. Next, the entire surface of the coating film was exposed without using a mask at an exposure amount at which the residual film ratio was 80% using an exposure machine (“MPA-600FA” manufactured by Canon Inc .: using an ultra-high pressure mercury lamp). Next, a development process was performed at 25 ° C. by a liquid piling method using a tetramethylammonium hydroxide aqueous solution (developer) having a concentration of 2.38% by mass. The development processing time was 100 seconds. After the development treatment, the coating film was washed with running ultrapure water for 1 minute and dried to form a pattern on the glass substrate. This glass substrate was heated in a clean oven at 230 ° C. for 30 minutes to obtain a cured film. The transmittance of this cured film was evaluated according to the following criteria.
A: Average transmittance of 380-780 nm is 99% or more B: Average transmittance of 380-780 nm is 95% or more and less than 99% C: Average transmittance of 380-780 nm is less than 95%

[Multi-exposure stability]
Line and space ratio (L / S) is 4: 1 (line width is 400 [mu] m, the space width is 100 [mu] m) using a mask, exposure once with exposure 1000 J / ^{m 2,} at an exposure amount 500 J / ^{m 2} 2 A cured film (interlayer insulating film) was formed in the same manner as the evaluation of the residue, except that the exposure was performed twice or the exposure was performed twice at an exposure amount of 1000 J / m ² . The film thickness of the obtained cured film was measured with an optical interference type film thickness measuring device (“Lambda Ace VM-2210” manufactured by Screen Inc.). Calculating a cured film was exposed once with an exposure amount 1000 J / ^{m 2,} the thickness difference between the exposure of 500 J / ^{m 2} twice exposure, or exposure 1000 J / ^{m 2} twice exposed cured film, the following The stability of the multiple exposure area was evaluated according to the following criteria. When the film thickness difference was less than 0.05 μm, it was judged that the stability of the multiple exposure area was particularly good. In Table 2, the exposure amount 1000J and the cured film was exposed once / m ^2, exposure dose 500 J / m ² in the evaluation based on the difference of thickness between the two exposed cured film "multiple exposure unit stability and 1 ", and the cured film was exposed once with an exposure amount 1000 J / m ^2, the evaluation based on the difference in the thickness of the cured film was exposed twice at an exposure amount 1000 J / m ^2" multiple exposure unit stability 2 " It was.
(Evaluation criteria)
A: Film thickness difference is less than 0.05 μm B: Film thickness difference is 0.05 μm or more and less than 0.10 μm C: Film thickness difference is 0.10 μm or more

  As for each radiation sensitive resin composition of Examples 1-22, multiple exposure part stability 1 and 2 are A or B, and it turns out that generation | occurrence | production of the nonuniformity when multiple exposure arises can fully be suppressed. In addition, each of the radiation-sensitive resin compositions of Examples 1 to 22 is also A or B in terms of evaluation of resolution. That is, it turns out that the radiation sensitive resin composition of Examples 1-22 has multiple exposure part stability and resolution. On the other hand, the radiation sensitive resin composition of Comparative Example 1 was inferior in the multiple exposure part stability.

  Further, when compared in Examples 1 to 22, the sensitivity of Example 19 containing no compound (C) was slightly lower. Regarding the low residue property, Example 4 in which the ion-polymerizable group of the polymer (A) is not a cyclic ether group and Example 19 in which the compound (C) does not contain a compound resulted in a slightly low result. Regarding the development adhesion, Example 10 in which the polymerizable group of the (C) compound is not a cyclic ether group or (meth) acryloyl group, and Example 19 not containing the (C) compound resulted in a slightly lower result. It was. About the transmittance | permeability, Example 5 and 6 whose (B) ionic polymerization initiator is an ionic compound resulted in a slightly low result. Further, for example, comparison between Example 1 and Example 14 shows that when the polymer (A) has a predetermined cyclic hydrocarbon group, the stability of the multiple exposure area is further increased.

  The present invention can provide a radiation-sensitive resin composition capable of reducing exposure unevenness due to multiple exposure. Therefore, the radiation-sensitive resin composition reduces exposure unevenness even in a multiple exposure portion that may occur when a scanning exposure apparatus having a multiple exposure area is used. Therefore, the radiation sensitive resin composition of the present invention can be suitably used as a material for forming a cured film for a display element. In particular, the radiation-sensitive resin composition can be suitably used as a photosensitive material in the case of exposing a large substrate (for example, a 2200 mm × 2500 mm 10 generation substrate) with a scanning exposure apparatus.

Claims (10)

Forming a coating film on the substrate using the radiation-sensitive resin composition;
A step of multiply exposing at least a part of the coating film, and a step of developing the coating film,
The manufacturing method of the cured film for display elements in which the said radiation sensitive resin composition contains the polymer which has an ion polymerizable group, and at least 1 chosen from a photo-acid generator and a photobase generator.   The manufacturing method of the cured film of Claim 1 further equipped with the process of heating the said coating film after image development. The manufacturing method of the cured film for display elements of Claim 1 or Claim 2 in which the said polymer has a structural unit represented by following formula (1).

(In formula (1), R ¹ is a hydrogen atom or a methyl group. R ² is an oxiranyl group, a 3,4-epoxycyclohexyl group, a group represented by the following formula (2), an oxetanyl group, 3- An alkyloxetane-3-yl group or a vinyloxyalkoxy group, and X ¹ is a single bond, a methylene group or an alkylene group having 2 to 12 carbon atoms.)

(In formula (2), * represents a binding site with X ^1. )   The cured film for a display element according to claim 1, wherein the polymer further contains an alicyclic hydrocarbon group having 5 to 30 carbon atoms, a phenyl group, a benzyl group, or a combination thereof. Production method. The manufacturing method of the cured film for display elements of Claim 3 in which the said polymer further has a structural unit represented by following formula (3).

(In Formula (3), ^RA is a hydrogen atom or a methyl group. X is a C5-C30 alicyclic hydrocarbon group, a phenyl group, or a benzyl group.)   The method for producing a cured film for a display element according to claim 1, wherein at least one selected from the photoacid generator and the photobase generator is a nonionic compound.   The cured film for a display element according to any one of claims 1 to 6, wherein the radiation-sensitive resin composition further comprises a compound having a molecular weight of 2000 or less and having one or more polymerizable groups in one molecule. Manufacturing method. Used to manufacture a cured film for display elements by multiple exposure to at least a part,
A radiation-sensitive resin composition for display elements, comprising a polymer having an ionically polymerizable group and at least one selected from a photoacid generator and a photobase generator.   The cured film for display elements which is a hardened | cured material of the radiation sensitive resin composition of Claim 8.   A display element provided with the cured film for display elements of Claim 9.