JP6492444B2 - Radiation-sensitive resin composition, cured film, method for forming the same, and electronic device - Google Patents

Description

  The present invention relates to a radiation-sensitive resin composition, a polymer composition, a cured film, a method for forming the same, and an electronic device.

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

  As an example, Japanese Patent Application Laid-Open No. 2004-4669 aims to form a cured film for a display element with higher sensitivity than a positive radiation-sensitive resin composition using an acid generator such as naphthoquinonediazide. Positive chemical amplification materials have been proposed. 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, JP 2011-215596 A, and JP 2008-304902 A include an acid generator, an acetal structure and / or a ketal structure, and a resin having an epoxy group. Positive radiation sensitive compositions have been proposed.

  On the other hand, in recent years, organic EL elements have been desired to improve productivity, specifically, productivity of light-emitting layers and the like, for reasons such as panel enlargement and mass production for lighting applications. For this reason, in organic EL elements, as a method for forming a light emitting layer, a coating method such as ink jet coating, which is desired to improve productivity, is being promoted from a conventional vapor deposition method. Accordingly, as a material for forming the light emitting layer, a light emitting material corresponding to ink jet coating has been studied (Japanese Patent Laid-Open No. 11-54270).

  The formation of the light emitting layer by inkjet coating is performed, for example, by forming a bank (partition wall) for partitioning pixels and dropping ink into a pixel region (concave portion) surrounded by the bank (International Publication No. 2008/090828). . In such a method, when ink droplets are dropped on the pixel region, there is a possibility that the ink droplet overflows to the adjacent pixel region beyond the bank. Therefore, in order to suppress the overflow of ink droplets, it is necessary to take measures such as imparting ink affinity (hydrophilicity) to the substrate and imparting water repellency to the bank surface.

  However, as a material for forming the above bank, it has excellent water repellency and can be applied to panel enlargement, mass production, etc. (for example, coating film appearance characteristics and film thickness uniformity) and sufficient Have not been proposed.

JP 2001-354822 A JP 2004-4669 A JP 2004-264623 A JP 2011-215596 A JP 2008-304902 A Japanese Patent Laid-Open No. 11-54270 International Publication No. 2008/090828

  The present invention has been made based on the above circumstances, and provides a radiation-sensitive resin composition having excellent water repellency, good applicability, and sufficient radiation sensitivity. With the goal. The present invention further provides a polymer composition for preparing the radiation-sensitive resin composition, a cured film formed from the radiation-sensitive resin composition, a method for forming the polymer film, and an electronic device including the cured film. The purpose is to do.

  The invention made in order to solve the above problems includes a first structural unit containing an acid dissociable group (hereinafter also referred to as “structural unit (I)”) and a second structural unit containing a crosslinkable group (hereinafter referred to as “structural unit (I)”). And a polymer component (hereinafter also referred to as “structural unit (III)”) including at least one of a fluoroalkyl group and a group having a siloxane bond (hereinafter also referred to as “structural unit (III)”). Hereinafter, it is a radiation-sensitive resin composition containing “[A] polymer component”) and a radiation-sensitive acid generator (hereinafter also referred to as “[B] radiation-sensitive acid generator”).

  Another invention made in order to solve the above-described problem is that at least one of a first structural unit containing an acid dissociable group, a second structural unit containing a crosslinkable group, a group having a fluoroalkyl group and a siloxane bond is used. It is a polymer composition containing a polymer component having a third structural unit.

  The present invention further includes a cured film formed from the radiation-sensitive resin composition, and an electronic device including the cured film.

  The method for forming a cured film of the present invention includes 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 the radiation, and the development. It is a formation method of the cured film including the process of heating the applied coating film, Comprising: The said coating film is formed using the said radiation sensitive resin composition.

  The radiation-sensitive resin composition of the present invention has excellent water repellency, excellent coating properties (for example, the appearance characteristics of the coating film and uniformity of film thickness) and the like that can cope with the enlargement and mass production of panels. Satisfies radiation sensitivity. The present invention can further provide a cured film formed from the radiation-sensitive resin composition, a method for forming the cured film, and an electronic device including the cured film. Therefore, the radiation-sensitive resin composition, the cured film and the method for forming the same, and the electronic device can be suitably used for manufacturing processes of liquid crystal elements, organic EL elements, electronic circuits, sensors, and the like.

<Radiation sensitive resin composition>
The radiation-sensitive resin composition of the present invention contains [A] a polymer component and [B] a radiation-sensitive acid generator, and an antioxidant (hereinafter, also referred to as “[C] antioxidant”) as a suitable component. May be contained. Moreover, 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] The polymer component includes the structural unit (I), the structural unit (II), and the structural unit (III). The structural unit (III) includes a structural unit containing a fluoroalkyl group (hereinafter also referred to as “structural unit (III-1)”) and a structural unit containing a group having a siloxane bond (hereinafter referred to as “structural unit (III-2)”. ) ")) And the like.

  Since the [A] polymer component has the above structural unit, the radiation-sensitive resin composition has excellent radiation sensitivity and can improve water repellency of insulating films such as interlayer insulating films and light emitting element forming banks. It becomes possible. [A] The polymer component 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. In addition, the [A] polymer component may have two or more of each structural unit.

[A] The polymer component may include only one type of polymer, or may include a plurality of types of polymers, and the structural units (I) to (III) may be included in the plurality of types of polymers as a whole. You may go out. [A] Examples of the polymer component include (1) a polymer component including a polymer having the structural unit (I), the structural unit (II), and the structural unit (III-1);
(2) a polymer component including a polymer having the structural unit (I), the structural unit (II), and the structural unit (III-2);
(3) a polymer component including a polymer having the structural unit (I), the structural unit (II), the structural unit (III-1), and the structural unit (III-2);
(4) a polymer component comprising a polymer having the structural unit (I) and a polymer having the structural unit (II) and the structural unit (III-1);
(5) A polymer component comprising a polymer having the structural unit (I) and a polymer having the structural unit (II) and the structural unit (III-2);
(6) A polymer component comprising a polymer having the structural unit (I) and a polymer having the structural unit (II), the structural unit (III-1) and the structural unit (III-2);
(7) A polymer component comprising a polymer having the structural unit (II) and a polymer having the structural unit (I) and the structural unit (III-1);
(8) A polymer component comprising a polymer having the structural unit (II) and a polymer having the structural unit (I) and the structural unit (III-2);
(9) A polymer component comprising a polymer having the structural unit (II) and a polymer having the structural unit (I), the structural unit (III-1) and the structural unit (III-2);
(10) A polymer component comprising a polymer having the structural unit (III) and a polymer having the structural unit (I), the structural unit (II) and the structural unit (III-2);
(11) Polymer components including a polymer having the structural unit (III-2) and a polymer having the structural unit (I), the structural unit (II), and the structural unit (III-1) are included.

  Hereinafter, the structural units (I) to (III) and other structural units will be described in detail.

[Structural unit (I)]
The structural unit (I) has an acid dissociable group. This acid-dissociable group acts as a protecting group for protecting a carboxy group, a phenolic hydroxyl group and the like in the polymer. A polymer having such a protective group is usually insoluble or hardly soluble in an alkaline aqueous solution. Since this protecting group is an acid-dissociable group, this polymer becomes soluble in an alkaline aqueous solution when the protecting group is cleaved by the action of an acid.

  In the radiation-sensitive resin composition, the [A] polymer component has the structural unit (I), thereby achieving high radiation sensitivity and improving the stability of the pattern shape obtained by development or the like. Become.

  As the structural unit (I) containing an acid dissociable group, a structural unit represented by the following formula (3) or the following formula (4) is preferable.

In the formula (3), R ¹⁷ is a hydrogen atom or a methyl group. R ¹⁸ and R ¹⁹ are each independently a hydrogen atom, a monovalent chain hydrocarbon group having 1 to 12 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms, or 4 to 20 carbon atoms. Are monovalent alicyclic hydrocarbon groups or groups in which some or all of the hydrogen atoms of these groups are substituted with fluorine atoms.

In Formula (4), R ²⁰ is a hydrogen atom or a methyl group. R ^{21 to} R ²⁷ are each independently a hydrogen atom, a monovalent chain hydrocarbon group having 1 to 12 carbon atoms, or a group in which part or all of the hydrogen atoms of the above group are substituted with fluorine atoms. is there. n is 1 or 2. When n is 2, the plurality of R ²⁶ and R ²⁷ may be the same or different.

Examples of the monovalent chain hydrocarbon group having 1 to 12 carbon atoms represented by R ¹⁸ and R ¹⁹ include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n -Linear alkyl groups such as hexyl group and n-octyl group; branched alkyl groups such as i-propyl group, i-butyl group, t-butyl group and neopentyl group.

Examples of the monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms represented by R ¹⁸ and R ¹⁹ include a phenyl group and a naphthyl group.

Examples of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by R ¹⁸ and R ¹⁹ include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, methyl Monocyclic cycloalkyl groups such as cyclohexyl and ethylcyclohexyl; cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclodecenyl, cyclopentadienyl, cyclohexadienyl, cyclooctadienyl Group, monocyclic cycloalkenyl group such as cyclodecadiene; bicyclo [2.2.2] octyl group, tricyclo [5.2.1.0 ^2,6 ] decyl group, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecyl group, norbornyl group, a polycyclic cycloalkyl group such as adamantyl group and the like.

A monovalent chain hydrocarbon group having 1 to 12 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms, and a monovalent alicyclic ring having 4 to 20 carbon atoms represented by R ¹⁸ and R ¹⁹ The formula hydrocarbon group may be substituted with a fluorine atom, but the number of fluorine atoms to be substituted is not particularly limited. When these groups are substituted with fluorine atoms, the water repellency of the unexposed part of the coating film of the radiation-sensitive resin composition is improved.

  Examples of the structural unit represented by the above formula (3) include structural units represented by the following formulas (3-1) to (3-28).

In the above formulas (3-1) to (3-28), R ¹⁷ has the same meaning as the above formula (3).

  Examples of the monomer that gives the structural unit represented by the formula (3) of the structural unit (I) include 1-ethoxyethyl methacrylate, 1-butoxyethyl methacrylate, 1- (tricyclodecanyloxy) methacrylate. Ethyl, 1- (pentacyclopentadecanylmethyloxy) ethyl methacrylate, 1- (pentacyclopentadecanyloxy) ethyl methacrylate, 1- (tetracyclododecanylmethyloxy) ethyl methacrylate, 1- (methacrylate Adamantyloxy) ethyl, pentafluoroethyloxyethylene methacrylate, heptafluoropropyloxyethylene methacrylate, nonafluorobutyloxyethylene methacrylate and the like.

In the above formula (4), examples of the monovalent chain hydrocarbon group having 1 to 12 carbon atoms represented by R ^{21 to} R ²⁷ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and the like. A linear alkyl group; a branched alkyl group such as i-propyl group, i-butyl group, sec-butyl group and t-butyl group; a linear alkenyl group such as ethenyl group and n-propenyl group A branched alkenyl group such as i-propenyl group and i-butenyl group;

The monovalent chain hydrocarbon group having 1 to 12 carbon atoms represented by R ^{21 to} R ²⁷ may be substituted with a fluorine atom, but the number of substituted fluorine atoms is not particularly limited. When these groups are substituted with fluorine atoms, the water repellency of the unexposed part of the coating film of the radiation-sensitive resin composition is improved.

  Examples of the structural unit represented by the above formula (4) include structural units represented by the following formulas (4-1) to (4-5).

In the above formulas (4-1) to (4-5), R ²⁰ has the same meaning as the above formula (4).

  As the monomer that gives the structural unit represented by the above formula (4), tetrahydro-2H-pyran-2-yl methacrylate that gives the structural unit represented by the above formula (4-3) is preferable.

  As a content rate of structural unit (I), 0.1 mol% or more is preferable with respect to all the structural units which comprise a [A] polymer component, 1 mol% or more is more preferable, and 10 mol% or more is further more preferable. On the other hand, the content is preferably 80 mol% or less, more preferably 60 mol% or less, and even more preferably 40 mol% or less.

[Structural unit (II)]
The structural unit (II) contains a crosslinkable group. The cured film formed from the radiation-sensitive resin composition has [A] polymer components having a structural unit (II) containing a crosslinkable group, so that the polymers constituting the [A] polymer components or [A] The strength can be increased by crosslinking the polymer constituting the polymer component with the [D] cyclic ether compound 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, an oxetanyl group, an alkoxymethyl group, a formyl group, an acetyl group, and a dialkylaminomethyl. Group, dimethylolaminomethyl group and the like.

  The crosslinkable group is preferably at least one selected from the group consisting of a (meth) acryloyl group, an oxiranyl group, and an oxetanyl group. Thereby, the intensity | strength of the cured film formed from the said radiation sensitive resin composition can be raised more.

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

In the above formula, R ²⁹ is a hydrogen atom or a methyl group.

As the monomer that gives the structural unit (II), a monomer containing a (meth) acryloyl group, an oxiranyl group or an oxetanyl group is preferred, a monomer containing an oxiranyl group or an oxetanyl group is more preferred, glycidyl methacrylate, 3-Methacryloyloxymethyl-3-ethyloxetane, 3,4-epoxycyclohexylmethyl methacrylate or 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate is more preferred.

  As a content rate of structural unit (II), 0.1 mol% or more is preferable with respect to all the structural units which comprise a [A] polymer component, and 1 mol% or more is more preferable. On the other hand, the content ratio is preferably 80 mol% or less, and more preferably 60 mol% or less. By making the content rate of structural unit (II) into the said range, the intensity | strength of the cured film formed can be raised effectively.

[Structural unit (III)]
The structural unit (III) includes at least one of a fluoroalkyl group and a group having a siloxane bond. The structural unit (III) includes a structural unit containing a fluoroalkyl group (hereinafter also referred to as “structural unit (III-1)”) and a structural unit containing a group having a siloxane bond (hereinafter referred to as “structural unit (III-2)”. ) ")) And the like.

(Structural unit III-1)
The structural unit (III-1) contains a fluoroalkyl group (except for those corresponding to the structural unit (I) containing an acid dissociable group). A fluoroalkyl group is one in which one or more hydrogen atoms of an alkyl group are substituted with fluorine atoms. Therefore, the structural unit (III-1) can exhibit water repellency with respect to a solvent or resin having a carboxyl group, a hydroxyl group, or an ester bond.

  The radiation-sensitive resin composition can improve the leveling properties of insulating films such as interlayer insulating films and light emitting element forming banks by having the structural unit (III-1) capable of exhibiting water repellency. It becomes. In addition, the radiation-sensitive resin composition improves coating properties by improving uneven coating on the substrate due to water repellency resulting from the structural unit (III-1), and is particularly advantageous for forming a coating film on a large substrate. It becomes.

  As the structural unit (III-1), a structural unit represented by the following formula (1) is preferable.

In formula (1), R ¹ is a hydrogen atom or a methyl group. R ² and R ³ are each independently a hydrogen atom, a trifluoromethyl group, a pentafluoroethyl group, a hydroxyl group, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. Or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms. a and b are each independently an integer of 0 to 12. When a is 2 or more, the plurality of R ² and the plurality of R ³ may be the same or different.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms represented by R ² and R ³ in the above formula (1) include an n-octyl group, a methylhexyl group, an ethylhexyl group, a cyclooctyl group, Examples thereof include a methylcyclohexyl group and a cyclohexylmethyl group.

The alkoxy group having 1 to 12 carbon atoms represented by R ² and R ^3, for example, methoxy, ethoxy, propoxy, butoxy, pentoxy, and the like.

Examples of the monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms represented by R ² and R ³ include a phenyl group and a naphthyl group.

R ² and R ³ are preferably a hydrogen atom, a pentafluoroethyl group, or a hydroxyl group.

  As said a, the integer of 0-2 is preferable.

  As said b, the integer of 0-4 is preferable.

  Examples of the structural unit (III-1) represented by the above formula (1) include structural units represented by the following formulas (1-1) to (1-12).

In the formulas (1-1) to (1-12), R ¹ has the same meaning as the formula (1).

  As a content rate of structural unit (III-1), 0 mol% or more is preferable with respect to all the structural units which comprise a [A] polymer component, and 1 mol% or more is more preferable. On the other hand, the content ratio is preferably 80 mol% or less, and more preferably 60 mol% or less. By setting the content ratio of the structural unit (III-1) in the above range, it is possible to achieve both higher levels of water repellency and applicability of an insulating film such as a bank formed from the radiation-sensitive resin composition. it can.

(Structural unit (III-2))
The structural unit (III-2) includes a group having a siloxane bond. A group having a siloxane bond exhibits water repellency. Therefore, similarly to the structural unit (III-1) containing a fluoroalkyl group, the structural unit (III-2) can exhibit water repellency with respect to a solvent or a resin having a carboxyl group, a hydroxyl group, or an ester group.

  The radiation-sensitive resin composition can improve the water repellency of insulating films such as interlayer insulating films and light emitting element forming banks by having the structural unit (III-2) capable of exhibiting water repellency. It becomes. In addition, the radiation-sensitive resin composition improves coating properties by improving coating unevenness on the substrate due to leveling properties derived from the structural unit (III-2), and is particularly advantageous for forming a coating film on a large substrate. It becomes.

  As the structural unit (III-2), a structural unit represented by the following formula (2) is preferable.

In formula (2), R ⁴ is a hydrogen atom or a methyl group. R ⁵ and R ⁶ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a monovalent aromatic group having 6 to 15 carbon atoms. It is a hydrocarbon group. R ⁷ and R ⁸ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or a group represented by the following formula (2-1). R ^{9 to} R ¹¹ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. c and d are each independently an integer of 0 to 12. When c is 2 or more, the plurality of R ⁵ and the plurality of R ⁶ may be the same or different. When d is 2 or more, the plurality of R ⁷ and the plurality of R ⁸ may be the same or different.

In formula (2-1), R ^{12 to} R ¹⁶ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or a monovalent aromatic carbon group having 6 to 12 carbon atoms. It is a hydrogen group. e is an integer of 1-12. When e is 2 or more, the plurality of R ¹² and the plurality of R ¹³ may be the same or different from each other. * Represents a bonding site with the silicon atom to which R ⁷ and R ⁸ in the formula (2) are bonded.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms represented by R ^{5 to} R ¹¹ in the above formula (2) include, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, n -Linear alkyl groups such as -pentyl group, n-hexyl group and n-octyl group; branched alkyl groups such as i-propyl group, i-butyl group, t-butyl group and neopentyl group.

Examples of the alkoxy group having 1 to 12 carbon atoms represented by R ⁵ and R ⁶ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group. Is mentioned.

Examples of the monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms represented by R ⁵ and R ⁶ include a phenyl group and a naphthyl group.

Examples of the monovalent aliphatic hydrocarbon group ^R 12 1 to 12 carbon atoms represented by ^{to R 16,} those similar to the groups exemplified as the above ^R 5 ^{to R 11} can be mentioned.

Examples of the monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms represented by R ^{12 to} R ¹⁶ include a phenyl group and a naphthyl group.

  Examples of the monomer that gives the structural unit (III-2) represented by the above formula (2) include monomers represented by the following formulas (2-A) to (2-F).

  In formulas (2-A) to (2-F), f, g and h are integers of 1 to 12.

  As a content rate of structural unit (III-2), 0 mol% or more is preferable with respect to all the structural units which comprise a [A] polymer component, and 1 mol% or more is more preferable. On the other hand, the content ratio is preferably 80 mol% or less, more preferably 60 mol% or less, and the content ratio of (III-2) within the above range makes it possible to form a bank formed from the radiation-sensitive resin composition. Both the water repellency and the coating property of the insulating film can be achieved.

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

  Other monomers that give structural units include, for example, unsaturated carboxylic acids and anhydrides thereof, (meth) acrylic acid esters having hydroxyl groups, (meth) acrylic acid chain alkyl esters, (meth) acrylic acid alicyclics. Examples include esters, (meth) acrylic acid aryl esters, unsaturated aromatic compounds, N-substituted maleimides, conjugated dienes, and unsaturated compounds having a tetrahydrofuran skeleton.

Examples of unsaturated carboxylic acids and anhydrides thereof include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid, or Its anhydride;
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 or anhydrides thereof.

  Among these, an anhydride of unsaturated monocarboxylic acid or unsaturated dicarboxylic acid is preferable, and (meth) acrylic acid or maleic anhydride is more preferable from the viewpoint of copolymerization reactivity, solubility in an alkaline aqueous 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, 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, methacrylic acid. N-lauryl acid, tridecyl methacrylate, 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-stearyl acrylate, and the like.

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 aryl 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, and p-methoxystyrene.

  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. .

  The content ratio of other structural units is usually 50 mol% or less with respect to all the structural units constituting the [A] polymer component, and the upper limit is preferably 30 mol%, more preferably 25 mol%. . On the other hand, the lower limit is preferably 5 mol%, more preferably 10 mol%. By setting the content ratio of other structural units in the above range, a radiation-sensitive resin composition that optimizes solubility in an alkaline aqueous solution and is superior in radiation sensitivity can be obtained.

<[A] Polymer component synthesis method>
[A] The polymer component can be produced, for example, by polymerizing a monomer corresponding to a predetermined structural unit in a suitable solvent using a radical polymerization initiator. For example, a method of dropping a solution containing a monomer and a radical initiator into a reaction solvent or a solution containing the monomer to cause a polymerization reaction, a solution containing the monomer, and a solution containing the radical initiator A method in which a polymerization reaction is carried out by dropping the reaction solution into a solution containing a reaction solvent or a monomer, a plurality of types of solutions each containing a monomer, and a solution containing a radical initiator are reacted separately. It is preferable to synthesize by a method such as a method of dropping a solvent or a monomer-containing solution to cause a polymerization reaction.

  [A] Examples of the solvent used for the polymerization reaction of the polymer component include the same solvents as those exemplified in the section “<Preparation of Radiation Sensitive Resin Composition>” described below.

  As the 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 (2 , 4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (methyl 2-methylpropionate), etc .; benzoyl peroxide , Organic peroxides such as lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) cyclohexane; hydrogen peroxide and the like.

  [A] In the polymerization reaction of the polymer component, 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; Xanthogens such as xanthogen sulfide and diisopropylxanthogen disulfide; terpinolene, α-methylstyrene dimer and the like.

[A] The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer is preferably 2.0 × 10 ³ or more and 1.0 × 10 ⁵ or less, and preferably 5.0 × 10 ³ or more. 5.0 × 10 ⁴ or less is more preferable. [A] By making Mw of a polymer component into the said range, the radiation sensitivity and developability of the said radiation sensitive resin composition can be improved.

[A] The number average molecular weight (Mn) in terms of polystyrene by GPC of the polymer component is preferably 2.0 × 10 ³ or more and 1.0 × 10 ⁵ or less, and 5.0 × 10 ³ or more and 5.0 × 10 ^4. The following is more preferable. [A] By making Mn of a polymer into the said range, the cure reactivity at the time of hardening of the coating film of the said radiation sensitive resin composition can be improved.

  [A] The molecular weight distribution (Mw / Mn) of the polymer component is preferably 3.0 or less, and more preferably 2.6 or less. [A] By making Mw / Mn of a polymer component into the said range, the sensitivity of the cured film obtained can be improved.

<[B] Radioactive acid generator>
[B] The radioactive 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. When the radiation-sensitive resin composition contains the [B] radiation-sensitive acid generator, the radiation-sensitive resin composition can exhibit radiation-sensitive characteristics and can have good radiation sensitivity. . The inclusion form of the [B] radiation-sensitive acid generator in the radiation-sensitive resin composition is a compound form (hereinafter 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 polymer constituting the polymer component, or in both forms. These [B] radioactive acid generators may be used alone or in combination of two or more.

  [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.

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

In formula (5), R ²⁸ represents an alkyl group, a monovalent alicyclic hydrocarbon group, an aryl group, or a group in which part or all of the hydrogen atoms of these groups have been substituted with a substituent.

The alkyl group represented by R ²⁸ is preferably a linear or branched alkyl group having 1 to 12 carbon atoms.

The monovalent alicyclic hydrocarbon group represented by R ²⁸ is preferably an alicyclic hydrocarbon group having 4 to 12 carbon atoms.

The aryl group represented by R ²⁸ is preferably an aryl group having 6 to 20 carbon atoms, and 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 a group represented by the above formula (5) include oxime sulfonate compounds represented by the following formulas (5-1) to (5-3).

R < ²⁸ > is synonymous with the said Formula (5) in said Formula (5-1)-(5-3). The formula (5-1) and formula ^{(5-2), R 30} represents an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms. In formula (5-3), X 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, a plurality of X may be the same or different.

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

  Examples of the oxime sulfonate compound represented by the above (5-3) include compounds represented by the following formulas (5-4) to (5-8).

  The compounds represented by the above formulas (5-4) to (5-8) are respectively (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-octyl). Sulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-p-toluene) They are sulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile and (2- (octylsulfonyloxyimino) -2- (4-methoxyphenyl) acetonitrile, which are commercially available.

[N-sulfonyloxyimide compound]
Examples of the N-sulfonyloxyimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethyl). Phenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) Phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) Phenylmaleimide, 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 [2.2 1] Hept-5-ene-2,3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (camphorsulfonyl) Oxy) -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) B) 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-dicarboximide 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- (phenylsulfonyl) Oxy) naphthyl dicarboximide, N- (2-trifluoromethylphenyl) 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) naphthy Rudicarboximide, N- (octylsulfonyloxy) naphthyl dicarboximide, N- (nonylsulfonyloxy) naphthyl dicarboximide and the like.

  As the onium salt, the halogen-containing compound, the diazomethane compound, the sulfone compound, the sulfonic acid ester compound, the carboxylic acid ester compound, and the like, the compounds described in JP 2011-232632 A can be used.

  [B] The radiation-sensitive acid generator is preferably an oxime sulfonate compound or an N-sulfonyloxyimide 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 (5-4)-(5-8) is more preferable.

  The said radiation sensitive resin composition can improve radiation sensitivity by using the compound illustrated as a [B] radiation sensitive acid generator.

  [B] The content of the radioactive acid generator is preferably 0.1 parts by mass or more and more preferably 1 part by mass or more with respect to 100 parts by mass of the polymer component [A]. On the other hand, as said content, 10 mass parts or less are preferable, and 5 mass parts or less are more preferable. [B] By making content of a radiation sensitive acid generator into the said range, the sensitivity of the said radiation sensitive resin composition can be optimized, and a cured film with high surface hardness can be formed, 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.

  By containing the [C] antioxidant, the radiation-sensitive resin composition suppresses the degradation degradation of the polymer molecules in the cured film formed from the radiation-sensitive resin composition, and the light resistance, etc. Can be improved.

  [C] Examples of the antioxidant include a compound having a hindered phenol structure, a compound having a hindered amine structure, a compound having an alkyl phosphite structure, and a compound having a thioether structure. These [C] antioxidants may be used alone or in combination of two or more.

  Examples of the compound having a hindered phenol structure include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- (3,5-di-). tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tris- (3,5-di-tert-butyl-4-hydroxy Benzyl) -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 ′, 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, -Triazin-2-ylamine) phenol, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} 2,4 , 8,10-tetraoxaspiro [5,5] -undecane and the like.

Examples of commercially available compounds having the hindered phenol structure include “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” (hereinafter, ADEKA), “SUMILIZER GM”, “SUMILIZER GS”, “SUMILIZER MDP-S”, “SUMILIZER BBM-S”, “SUMILZER” R "," sumilizer GA-80 "(manufactured by Sumitomo Chemical);
"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.

  In these, as [C] antioxidant, it is preferable to have a hindered phenol structure. [C] When the antioxidant has a hindered phenol structure, the degradation degradation of the polymer molecules in the cured film formed from the radiation-sensitive resin composition can be further suppressed. Among compounds having a hindered phenol structure, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] or tris- (3,5-di-tert-butyl- 4-Hydroxybenzyl) -isocyanurate is more 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 cured film formed from the said radiation sensitive resin composition can be suppressed more effectively.

<Other optional components>
In addition to the components [A] to [C], the radiation-sensitive resin composition includes a compound [D] having a cyclic ether group, and [E] acid diffusion as long as the effects of the present invention are not impaired. Other optional components such as a control agent, [F] surfactant, [G] adhesion assistant, and [H] solvent 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] Compound having cyclic ether group>
[D] A compound having a cyclic ether group (hereinafter also referred to as “[D] compound”) is a compound having a cyclic ether group and different from the polymer of the [A] polymer component. The radiation-sensitive resin composition contains the [D] compound, thereby promoting the crosslinking of the [A] polymer component and the like by the thermal reactivity of the [D] compound, and formed from the radiation-sensitive resin composition. The hardness of the cured film can be further increased, and the radiation sensitivity of the radiation-sensitive resin composition can be increased.

  [D] As the compound, a compound having two or more epoxy groups (oxiranyl group, oxetanyl group) in the molecule is preferable.

Examples of the compound having two or more oxiranyl groups in the molecule include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, Bisphenol type diglycidyl ethers such as hydrogenated bisphenol AD diglycidyl ether;
Polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether Glycidyl ethers;
Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin;
Phenol novolac type epoxy resin;
Cresol novolac type epoxy resin;
Polyphenol type epoxy resin;
Diglycidyl esters of aliphatic long-chain dibasic acids;
Glycidyl esters of higher fatty acids;
Aliphatic polyglycidyl ethers;
Examples include epoxidized soybean oil and epoxidized linseed oil. These [D] compounds may be used alone or in combination of two or more.

Commercially available products of [D] compounds having two or more oxiranyl groups in the molecule include, for example, “Epicoat 1001”, “Epicoat 1002”, “Epicoat 1003”, “Epicoat 1004”, “ “Epicoat 1007”, “Epicoat 1009”, “Epicoat 1010”, “Epicoat 828” (Japan Epoxy Resin Co., Ltd.), etc .;
As bisphenol F type epoxy resin, “Epicoat 807” (Japan Epoxy Resin Co., Ltd.) and the like;
Examples of phenol novolac type epoxy resins include “Epicoat 152”, “Epicoat 154”, “Epicoat 157S65” (Japan Epoxy Resin Co., Ltd.), “EPPN201”, “EPPN202” (Japan Nippon Kayaku Co., Ltd.) and the like;
Examples of cresol novolac type epoxy resins include “EOCN102”, “EOCN103S”, “EOCN104S”, “EOCN1020”, “EOCN1025”, “EOCN1027” (Nippon Kayaku Co., Ltd.), Epicort 180S75 (Japan Epoxy Resin), etc .;
As the polyphenol type epoxy resin, “Epicoat 1032H60”, “Epicoat XY-4000” (Japan Epoxy Resin Co., Ltd.) and the like;
Cycloaliphatic epoxy resins include “CY-175”, “CY-177”, “CY-179”, “Araldite CY-182”, “Araldite 192”, “Araldite 184” (above, Ciba Specialty Chemicals) ), “ERL-4234”, “ERL-4299”, “ERL-4221”, “ERL-4206” (above U.C.C.), “Shaudyne 509” (Showa Denko), “Epicron 200” ”,“ Epicron 400 ”(above, Dainippon Ink Co., Ltd.),“ Epicoat 871 ”,“ Epicoat 872 ”(above, Japan Epoxy Resin Co., Ltd.),“ ED-5661 ”,“ ED-5562 ”(above, Celanese Coating) Etc.);
Examples of the aliphatic polyglycidyl ether include “Epolite 100MF” (Kyoeisha Chemical Co.), “Epiol TMP” (Nippon Yushi Co., Ltd.) and the like.

  Examples of the [D] compound having two or more oxetanyl groups in the molecule include bis [(3-ethyloxetane-3-yl) methyl] isophthalate, 1,4-bis [(3-ethyloxetane-3- Yl) methoxymethyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, di [1-ethyl- (3-oxetanyl) methyl] ether (also known as bis (3-ethyl-) 3-oxetanylmethyl) ether), 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-[1,3- (2-methylenyl) propanediylbis (oxymethylene)] bis- (3-ethyloxetane), 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanyl) Toxi) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethyleneglycolbis (3-ethyl-3-oxetanylmethyl) ) Ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ) Ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, xylenebisoxetane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3) - Cetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether Dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ) Ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3-) Oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl) -3-Oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether, and the like.

  Among these, as the [D] compound, a compound having two or more oxetanyl groups in the molecule is preferable, and bis [(3-ethyloxetan-3-yl) methyl] isophthalate or 1,4-bis [ (3-Ethyloxetane-3-yl) methoxymethyl] benzene is more preferred.

  [D] The content of the compound is usually 150 parts by mass or less, preferably 0.5 parts by mass or more and 100 parts by mass or less, and preferably 1 part by mass or more and 50 parts by mass with respect to 100 parts by mass of the polymer component [A]. Is more preferably 10 parts by mass or more and 25 parts by mass or less. [D] By making content of a compound into the said range, the hardness of the cured film formed from the said radiation sensitive resin composition can be raised more.

<[E] acid diffusion controller>
[E] The acid diffusion control agent can be arbitrarily selected from those used in chemically amplified resists. The radiation-sensitive resin composition contains an [E] acid diffusion control agent, whereby the diffusion length of the acid generated from the [B] radiation-sensitive acid generator by exposure can be appropriately controlled, and pattern development Can be improved.

  [E] As the acid diffusion control agent, an acid diffusion control agent described in JP2011-232632 can be used.

  [E] The content of the acid diffusion controller 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. More preferably, it is not less than 0.2 parts by mass. [E] By making content of an acid diffusion control agent 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 said radiation sensitive resin composition can improve the surface smoothness of a coating film by containing [F] surfactant, As a result, the film thickness of the cured film formed from the said radiation sensitive resin composition Uniformity can be further improved.

  [F] Examples of the surfactant include a fluorine-based surfactant and a silicone-based surfactant. These [F] surfactants may be used alone or in combination of two or more. [F] As the surfactant, surfactants described in JP 2011-18024 A can be used.

  [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 a film-forming object such as a substrate and a cured film. [G] The adhesion aid is particularly useful for improving the adhesion between the inorganic substrate and the cured 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 the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltri Examples include methoxysilane, 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 or 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 formed cured film and the substrate is further improved.

<[H] solvent>
[H] 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 the [H] solvent 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 propio. Nates, aromatic hydrocarbons, ketones, and other esters. [H] As the solvent, the solvents described in JP2011-232632 can be used.

<Method for preparing radiation-sensitive resin composition>
The radiation-sensitive resin composition is dissolved or dispersed by mixing the [A] polymer component and the [B] radiation-sensitive acid generator, a suitable component as necessary, and other optional components in a solvent. Prepared. For example, the said radiation sensitive resin composition can be prepared by mixing each component in a predetermined ratio in a solvent.

<Polymer composition>
The polymer composition of the present invention includes a first structural unit containing an acid dissociable group, a second structural unit containing a crosslinkable group, a structural unit containing a fluoroalkyl group, and a structural unit containing a group having a siloxane bond. A polymer component having at least one third structural unit selected from the group consisting of: This polymer component is the same as the [A] polymer component of the radiation-sensitive resin composition. Even if the polymer component includes the first structural unit, the second structural unit, and the third structural unit in the same polymer, the first structural unit, the second structural unit in different polymers, And a third structural unit. Since the said polymer composition contains the polymer component similar to a [A] polymer component, it can be used conveniently for preparation of the said radiation sensitive resin composition.

<Curing film>
The cured film of the present invention is formed from the radiation sensitive resin composition. Since the said cured film is formed from the said radiation sensitive resin composition, it has the outstanding water repellency, the external appearance characteristic of a coating film, and the uniformity of a film thickness. The cured film having such characteristics includes, for example, banks (partitions), spacers, protective films, and color filters that define regions for forming interlayer insulating films, planarization films, and light emitting layers of electronic devices such as display elements. It can be used for coloring patterns. In addition, although it does not specifically limit as a formation method of the said cured film, It is preferable to apply the formation method of the cured film demonstrated below.

<Method for forming cured film>
The said radiation sensitive resin composition can be used suitably for formation of a cured film.

  The method for forming a cured film of the present invention includes a step of forming a coating film on a substrate using the radiation-sensitive resin composition (hereinafter also referred to as “step (1)”), and at least a part of the coating film. A step of irradiating radiation (hereinafter also referred to as “step (2)”), a step of developing a coating film irradiated with radiation (hereinafter also referred to as “step (3)”), and heating the developed coating film (Hereinafter, also referred to as “step (4)”).

  According to the method for forming a cured film, a cured 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, a cured film having a fine and elaborate pattern can be easily formed by forming a pattern by exposure, development and heating utilizing photosensitivity.

[Step (1)]
In this step, the radiation-sensitive resin composition is used and 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 a cyclic olefin, and a hydrogenated product thereof. Prebaking conditions vary depending on the type of each component, the blending ratio, and the like, but are usually 70 ° C. or higher and 120 ° C. or lower and 1 minute or longer and 10 minutes or shorter.

[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. The radiation used for exposure is preferably radiation having a wavelength in the range of 190 nm or more and 450 nm or less, and more preferably radiation containing ultraviolet light of 365 nm. The exposure amount is preferably 500 J / ^{m 2} or more, 1,500J / ^{m 2} or more is more preferable. On the other hand, preferably 6,000J / ^{m 2} or less as the exposure amount, 1,800J / ^{m 2} or less 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, and a shower method. 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, after washing with running water for 30 seconds or more and 90 seconds or less, 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, the patterned thin film is heated using a heating device such as a hot plate or an oven, whereby the curing reaction of the polymer component [A] can be promoted to form a cured film. As heating temperature, it is about 120 degreeC or more and 250 degrees C or less, for example. The heating time varies depending on the type of heating device, but for example, it is about 5 minutes to 30 minutes for a hot plate, and about 30 minutes 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 desired cured film can be formed on the surface of the substrate. The thickness of the cured film is preferably 0.05 μm or more, on the other hand, preferably 8 μm or less, more preferably 6 μm or less.

<Electronic device>
The electronic device of the present invention includes the cured film. The electronic device is, for example, a liquid crystal display element or an organic EL display element.

  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 cured film, the liquid crystal display element is excellent in reliability such as heat resistance.

  As a manufacturing method of a liquid crystal 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 “<Method for forming cured film>”, an interlayer insulating film, a spacer, a protective film, or both are 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. And as an electronic device of the present invention, 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 interlayer insulating film, a protective film, a spacer, or both, 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 an electronic device 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 cured 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 these Examples. In addition, the weight average molecular weight (Mw) of [A] polymer component was measured with the following method.

[Weight average molecular weight (Mw)]
It measured by gel permeation chromatography (GPC) under the following conditions.
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

<[A] Synthesis of polymer component>
[Synthesis Example 1] (Synthesis of polymer (A-1))
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 10 parts by weight of methacrylic acid, 50 parts by weight of 1-butoxyethyl methacrylate as a monomer giving structural unit (I), and 3-methacryloyloxymethyl-3-ethyl as a monomer giving structural unit (II) After 30 parts by mass of oxetane and 20 parts by mass of 2,2,2-trifluoroethyl methacrylate as a monomer giving structural unit (III) 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 polymer (A-1). The polystyrene equivalent weight average molecular weight (Mw) of the polymer (A-1) was 9,000. The solid content concentration of the polymer solution obtained here was 31.4% by mass.

[Synthesis Example 2] (Synthesis of polymer (A-2))
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 10 parts by weight of methacrylic acid, 40 parts by weight of tetrahydro-2H-pyran-2-yl methacrylate as a monomer giving structural unit (I), and 45 parts by weight of glycidyl methacrylate as a monomer giving structural unit (II) Part 5 and 5 parts by mass of the compound represented by the above formula (2-A) as a monomer giving the structural unit (III) were charged and purged with nitrogen, and then gently stirred. 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-2). The polymer (A-2) had a weight average molecular weight (Mw) in terms of polystyrene of 8,500. The solid content concentration of the polymer solution obtained here was 32.6% by mass.

[Synthesis Example 3] (Synthesis of Polymer (A-3))
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 40 parts by mass of nonafluorobutyloxyethylene methacrylate as a monomer giving structural unit (I), 40 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate as monomer giving structural unit (II) and structural unit ( After adding 20 parts by mass of 2,2,3,3,3-pentafluoropropane methacrylate as a monomer to give III) 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 polymer (A-3). The polymer (A-3) had a polystyrene equivalent weight average molecular weight (Mw) of 11,000. The solid content concentration of the polymer solution obtained here was 32.4% by mass.

[Synthesis Example 4] (Synthesis of Polymer (A-4))
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 50 parts by mass of tetrahydro-2H-pyran-2-yl methacrylate, 35 parts by mass of benzyl methacrylate and 15 parts by mass of hydroxyethyl methacrylate were charged as a monomer to give the structural unit (I), and after nitrogen substitution, the mixture was gently stirred. 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 the polymer (A-4). The polystyrene equivalent weight average molecular weight (Mw) of the polymer (A-4) was 10,500. The solid content concentration of the polymer solution obtained here was 31.8% by mass.

[Synthesis Example 5] (Synthesis of Polymer (A-5))
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 60 parts by mass of glycidyl methacrylate as a monomer giving structural unit (II), 20 parts by mass of styrene and 20 masses of 2,2,2-trifluoroethyl methacrylate as monomers giving structural unit (III) After the part 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 polymer (A-5). The polymer (A-5) had a polystyrene equivalent weight average molecular weight (Mw) of 10,000. The solid content concentration of the polymer solution obtained here was 32.0% by mass.

[Comparative Synthesis Example 1] (Synthesis of polymer (a-1))
In this comparative synthesis example, a polymer was synthesized without using any monomer that gave the structural unit (III-1) containing a fluoroalkyl group and the structural unit (III-2) having a group containing a siloxane bond. . A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 10 parts by weight of methacrylic acid, 50 parts by weight of 1-butoxyethyl methacrylate as a monomer giving structural unit (I), and 3-methacryloyloxymethyl-3-ethyl as a monomer giving structural unit (II) After 30 parts by mass of oxetane and 20 parts by mass of methyl methacrylate 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 polymer (a-1). The polystyrene equivalent weight average molecular weight (Mw) of the polymer (a-1) was 11,000. The solid content concentration of the polymer solution obtained here was 32.4% by mass.

<Preparation of radiation-sensitive resin composition>
[B] The radiation-sensitive acid generator, [C] antioxidant, [D] compound having a cyclic ether group and [E] acid diffusion controller used for the preparation of the radiation-sensitive resin composition are shown below.

([B] Radioactive 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 (6) ("IRGACURE PAG 203" manufactured by BASF)

  B-5: N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester

([C] antioxidant)
C-1: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (“Adeka Stub AO-60” manufactured by Adeka)
C-2: Tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate (“ADEKA STAB AO-20” from Adeka)
C-3: 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} 2,4,8,10- Tetraoxaspiro [5,5] -undecane (“Adeka Stub AO-80” from Adeka)
C-4: 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene (“Adeka Stub AO-330” from Adeka)

([D] Compound having cyclic ether group)
D-1: bis [(3-ethyloxetane-3-yl) methyl] isophthalate represented by the following formula (D-1)
D-2: 1,4-bis [(3-ethyloxetane-3-yl) methoxymethyl] benzene represented by the following formula (D-2)

([E] acid diffusion controller)
E-1: 4-Dimethylaminopyridine

[Example 1]
[A] To a polymer solution containing (A-1) as a polymer component (amount corresponding to 100 parts by mass (solid content) of (A-1)), [B] (B as a radioactive acid generator) -1) A radiation-sensitive resin composition was prepared by mixing 3 parts by mass and filtering with a membrane filter having a pore size of 0.2 μm.

[Examples 2 to 5 and Comparative Example 1]
A radiation-sensitive resin composition was prepared in the same manner as in Example 1 except that components of the types and blending amounts shown in Table 1 below were used. In addition, "-" in Table 1 indicates that the corresponding component was not blended.

[Example 6]
A polymer solution containing (A-4) (an amount corresponding to 50 parts by mass (solid content) of (A-4)) and a polymer solution containing (A-5) (50 parts by mass of (A-5) ( The amount corresponding to the solid content) is mixed to obtain the [A] polymer component, to which 3 parts by weight of (B-4) as the [B] radioactive acid generator is mixed, A radiation sensitive resin composition was prepared by filtering through a 2 μm membrane filter.

[Example 7]
A polymer solution containing (A-4) (amount corresponding to 70 parts by mass (solid content) of (A-4)) and a polymer solution containing (A-5) (30 parts by mass of (A-5) ( The amount corresponding to the solid content) is mixed to obtain [A] a polymer component, and [B] (B-5) 3 parts by mass as a radioactive acid generator, and [C] an antioxidant as an antioxidant. (C-2) 1 part by mass, (D-1) 10 parts by mass as an antioxidant and (E) 0.1 part by mass of (E-1) as an acid diffusion controller were mixed, A radiation sensitive resin composition was prepared by filtering through a membrane filter having a pore size of 0.2 μm.

<Evaluation>
Using the radiation-sensitive resin compositions of Examples 1 to 7 and Comparative Example 1, evaluation of radiation sensitivity, coating film appearance, film thickness uniformity, light resistance, transmittance and water repellency was carried out. The evaluation results are also shown in Table 1.

[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 second 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 radiation sensitivity is good.

[Evaluation of appearance of coating film]
A radiation sensitive composition is applied onto a 550 × 650 mm chromium film using a slit die coater (“R6322105-CL” from Tokyo Ohka Kogyo Co., Ltd.), the ultimate pressure is set to 100 Pa, and the solvent is removed under vacuum. Then, the film was further pre-baked at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The appearance of this coating film was observed with the naked eye under a sodium lamp. At this time, the appearance state was investigated, assuming that the haze-like unevenness generated in the entire coating film was “moy unevenness” and the unevenness derived from the proxy pin of the pre-baking furnace was “pin unevenness”. The case where almost none of these unevennesses were visible was evaluated as “◯” (excellent), the case where any of these unevennesses was slightly visible was “△” (good), and the case where they were clearly visible was evaluated as “x” (bad). .

[Evaluation of film thickness uniformity (uniformity)]
The film thickness uniformity was evaluated as uniformity. The uniformity was calculated from the film thickness at nine measurement points. The film thickness was measured using a needle contact measuring device (“AS200” from KLA Tencor) for the coating film prepared for the appearance evaluation. Nine measurement points are (275, 20), (275, 30), (275) where (X [mm], Y [mm]) is X when the minor axis direction of the substrate is X and the major axis direction is Y. , 60), (275, 100), (275, 325), (275, 550), (275, 590), (275, 620), and (275, 630). The calculation of uniformity was performed based on the following mathematical formula.

Uniformity (%) =
{FT (X, Y) max-FT (X, Y) min} × 100 / {2 × FT (X, Y) avg. }
(In the above formula, FT (X, Y) max is the maximum value in the film thickness at nine measurement points, FT (X, Y) min is the minimum value in the film thickness at nine measurement points, and FT (X, Y Y) avg. Is an average value in the film thickness at nine measurement points.)

  The film thickness uniformity can be judged good when the uniformity is 5% or less.

[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 a cured film. In the light resistance evaluation, since the patterning of the cured film is unnecessary, the exposure process and the development process are omitted, and the cured film is formed only by the coating film forming process and the heating process.

This cured film was irradiated with UV light having an illuminance of 130 mW, an exposure intensity of 800,000 J / m ² , and a peak wavelength of 365 nm using a UV irradiation apparatus (Ushio Corporation “UVX-02516S1JS01”). It can be said that the light resistance of the cured film is good when the amount of film thickness reduction after irradiation is 3% or less compared to the film thickness before irradiation.

[Evaluation of transmittance]
A coating film was formed on a glass substrate using the radiation-sensitive resin composition by the same method as the light resistance evaluation. This glass substrate was heated at 220 ° C. for 1 hour in a clean oven to form a cured film. About this cured film, the transmittance | permeability in wavelength 400nm was measured using the spectrophotometer ("150-20 type double beam" of Hitachi, Ltd.). It can be said that the transparency is poor when the transmittance is less than 90%.

[Evaluation of water repellency]
After coating the radiation-sensitive compositions prepared in Examples 1 to 7 or Comparative Example 1 on a silicon substrate with a spinner, the coating film is 3.0 μm thick by pre-baking on a 90 ° C. hot plate for 2 minutes. Formed. Next, the obtained coating film was irradiated with radiation using a high pressure mercury lamp through a quartz mask (contact) using an exposure machine (Canon “MPA-600FA” (ghi line mixing)) with an exposure dose of 500 J / m ^2. Irradiation was performed. Then, it developed by the piling method for 80 second at 25 degreeC with 0.5 mass% tetramethylammonium hydroxide aqueous solution. Subsequently, running water was washed with ultrapure water for 1 minute, and then dried to form a pattern. Then, by baking for 30 minutes at 220 ° C. using a hot plate, the exposed part becomes a lyophilic part, and a film other than the exposed part becomes a lyophobic part. A film patterned by the lyophilic part and the lyophobic part is formed. did. In the formed lyophobic patterning film, using a contact angle meter (“CA-X” from Kyowa Interface Science Co., Ltd.), the coating surface of the exposed portion corresponding to the lyophilic portion, and the unexposed portion corresponding to the lyophobic portion. The contact angle of water on each coating film surface was measured.

  As is clear from the results in Table 1, the radiation sensitive resin compositions of Examples 1 to 7 are excellent in radiation sensitivity, and the cured film formed from these radiation sensitive resin compositions has a coating appearance and a film thickness. It was excellent in uniformity, light resistance, transmittance and contact angle (water repellency).

  On the other hand, although the radiation sensitive resin composition of Comparative Example 1 is excellent in radiation sensitivity, the cured film formed from this radiation sensitive resin composition has a poor external application. Compared with the cured film formed from the radiation-sensitive resin composition, the film thickness uniformity and water repellency were poor.

The radiation-sensitive resin composition of the present invention has excellent water repellency, excellent coating properties (for example, coating film appearance characteristics and film thickness uniformity) and the like that can be used for large panel size and mass production of panels. Satisfies radiation sensitivity. The present invention can further provide a cured film formed from the radiation-sensitive resin composition, a method for forming the cured film, and an electronic device including the cured film. Therefore, the radiation-sensitive resin composition, the cured film and the method for forming the cured film, and the electronic device can be suitably used for manufacturing processes of liquid crystal elements, organic EL elements, electronic circuits, sensors, and the like.

Claims (7)

A first polymer having a first structural unit containing an acid dissociable group,
A second polymer having a second structural unit containing a crosslinkable group and a third structural unit containing at least one of a fluoroalkyl group and a group having a siloxane bond, which is a polymer other than the first polymer, And a radioactive acid generator,
The first structural unit is at least one selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4):
The radiation sensitive resin composition in which the third structural unit is represented by the following formula (1) or the following formula (2).

(In Formula (3), R ¹⁷ is a hydrogen atom or a methyl group. R ¹⁸ and R ¹⁹ are each independently a hydrogen atom, a monovalent chain hydrocarbon group having 1 to 12 carbon atoms, carbon, A monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a group in which some or all of the hydrogen atoms of these groups are substituted with fluorine atoms It is.
In Formula (4), R ²⁰ is a hydrogen atom or a methyl group. R ^{21 to} R ²⁷ are each independently a hydrogen atom, a monovalent chain hydrocarbon group having 1 to 12 carbon atoms, or a group in which some or all of the hydrogen atoms of the above group are substituted with fluorine atoms. is there. n is 1 or 2. When n is 2, the plurality of R ²⁶ and the plurality of R ²⁷ may be the same or different. )

(In Formula (1), R ¹ is a hydrogen atom or a methyl group. R ² and R ³ are each independently a hydrogen atom, a trifluoromethyl group, a pentafluoroethyl group, a hydroxyl group, 12 is a monovalent aliphatic hydrocarbon group, an alkoxy group having 1 to 12 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms, wherein a and b are each independently 0 to 0; And is an integer of 12. When a is 2 or more, a plurality of R ^{2 s} and a plurality of R ^{3 s} may be the same or different.

(In Formula (2), R ⁴ is a hydrogen atom or a methyl group. R ⁵ and R ⁶ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or carbon. An alkoxy group having 1 to 12 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms, each of R ⁷ and R ⁸ independently represents a hydrogen atom or a monovalent fat having 1 to 12 carbon atoms; Or a group represented by the following formula (2-1): R ^{9 to} R ¹¹ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. c and d are each independently an integer of 0 to 12. When c is 2 or more, the plurality of R ⁵ and the plurality of R ⁶ may be the same or different, and d is 2 or more. for multiple R ⁷ and a plurality of R ^8, may each be the same or different. However, c is 1 or more Is an integer, and except where d is 0.)

(In Formula (2-1), R ^{12 to} R ¹⁶ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or a monovalent aromatic group having 6 to 12 carbon atoms. E is an integer of 1 to ^12. However, when e is 2 or more, a plurality of R ^{12 s} and a plurality of R ^{13 s} may be the same or different. (It represents a bonding site with the silicon atom to which R ⁷ and R ⁸ in the above formula (2) are bonded)   The radiation-sensitive resin composition according to claim 1, wherein the crosslinkable group of the second structural unit is at least one selected from the group consisting of a (meth) acryloyl group, an oxiranyl group, and an oxetanyl group. The radiation sensitive resin composition of Claim 1 or Claim 2 in which the said radiation sensitive acid generator contains group represented by following formula (5).

(In formula (5), R ²⁸ is an alkyl group, a monovalent alicyclic hydrocarbon group, an aryl group, or a group obtained by substituting a part or all of the hydrogen atoms of these groups with a substituent. )   The radiation sensitive resin composition according to any one of claims 1 to 3, further comprising an antioxidant.   The cured film formed from the radiation sensitive resin composition of any one of Claims 1-4.   An electronic device comprising the cured film according to claim 5. A step of forming a coating film on the substrate; a step of irradiating at least a part of the coating film; a step of developing the coating film irradiated with the radiation; and a step of heating the developed coating film. A method for forming a cured film, comprising:
The formation method of the cured film which forms the said coating film using the radiation sensitive resin composition of any one of Claims 1-4.