JP6168212B2 - Positive radiation-sensitive resin composition, cured film and method for forming the same, semiconductor element, and display element - Google Patents

Description

  The present invention relates to a positive radiation sensitive resin composition, a cured film and a method for forming the same, a semiconductor element, and a display element.

  In recent years, flexible displays such as electronic paper have attracted attention, and plastic substrates using polyethylene terephthalate or the like have been studied as flexible display substrates. Since this substrate is stretched or shrunk when heated, the lowering of the manufacturing process is being studied, and in particular, the firing temperature in the process of forming a cured film such as an interlayer insulating film that is the highest temperature in the manufacturing process is required. ing.

  As a material for such a cured film capable of lowering the temperature, a radiation-sensitive resin composition having a small number of steps during pattern formation and high surface hardness is used. For example, a co-polymer containing a carboxy group and an epoxy group is used. A radiation-sensitive resin composition containing a coalescence is known, and is configured such that surface hardness as a cured film is obtained by the reaction of the carboxy group and the epoxy group (Japanese Patent Application Laid-Open No. 2001-354822). See the official gazette).

  However, in the radiation-sensitive resin composition containing the above-mentioned copolymer, the carboxy group and the epoxy group react even during storage of the radiation-sensitive resin composition, resulting in thickening. May reduce storage stability.

  Therefore, while maintaining good surface hardness, it is excellent in storage stability, and in addition, it is a cured film that can sufficiently satisfy general characteristics such as sensitivity, development adhesion, heat resistance, chemical resistance, transmittance and relative dielectric constant. There is a need for a radiation-sensitive resin composition capable of forming a.

JP 2001-354822 A

  The present invention has been made on the basis of the circumstances as described above, and the object thereof is excellent storage stability while maintaining good surface hardness, and in addition, sensitivity, development adhesion, heat resistance, chemical resistance It is to provide a positive-type radiation-sensitive resin composition capable of forming a cured film sufficiently satisfying general characteristics such as properties, transmittance, and dielectric constant.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、炭素数１〜４のアルキル基又は炭素数１〜４のフッ素化アルキル基である。但し、Ｒ^１及びＲ^２のうち、少なくともいずれかは、炭素数１〜４のフッ素化アルキル基である。
式（２）中、Ｒ^３及びＲ^４は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１〜４のアルキル基又は炭素数１〜４のフッ素化アルキル基である。但し、Ｒ^３及びＲ^４のうち、少なくともいずれかは、ハロゲン原子又は炭素数１〜４のフッ素化アルキル基である。） The invention made to solve the above problems is
[A] Structural unit (I) containing at least one selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2), and a cyclic ether structure or a cyclic carbonate structure A positive radiation-sensitive resin composition containing a polymer (hereinafter also referred to as “[A] polymer”) and a [B] acid generator.

(In Formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluorinated alkyl group having 1 to 4 carbon atoms, provided that R ¹ and R 2 are ^At least one of ² is a fluorinated alkyl group having 1 to 4 carbon atoms.
In Formula (2), R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluorinated alkyl group having 1 to 4 carbon atoms. However, at least one of R ³ and R ⁴ is a halogen atom or a fluorinated alkyl group having 1 to 4 carbon atoms. )

Moreover, another invention made in order to solve the said subject is:
A cured film formed from the positive-type radiation-sensitive resin composition,
A semiconductor element including the cured film; and a display element including the semiconductor element.

Furthermore, another invention made to solve the above problems is
(1) A step of forming a coating film on a substrate using the positive radiation sensitive resin composition,
(2) A step of irradiating a part of the coating film with radiation,
(3) A method for forming a cured film, comprising: a step of developing the coating film irradiated with the radiation; and (4) a step of heating the developed coating film.

  In addition to excellent storage stability while maintaining good surface hardness, the present invention sufficiently satisfies general characteristics such as sensitivity, development adhesion, heat resistance, chemical resistance, transmittance, and dielectric constant. A positive-type radiation-sensitive resin composition capable of forming a cured film that can be formed can be provided. Accordingly, the positive radiation sensitive resin composition, a cured film formed from the positive radiation sensitive resin composition, a semiconductor element and a display element, and a method for forming the cured film include electronic devices such as flexible displays, etc. It can be suitably used in the manufacturing process.

<Positive radiation sensitive resin composition>
The positive radiation sensitive resin composition of the present invention contains a [A] polymer and a [B] acid generator. Moreover, the said positive type radiation sensitive resin composition may contain a [C] solvent as a suitable component. Furthermore, the positive radiation sensitive resin composition may contain other optional components as long as the effects of the present invention are not impaired. Hereinafter, each component will be described in detail.

<[A] polymer>
[A] The polymer is a polymer having structural units (I) and (II). Moreover, the [A] polymer may have structural unit (III) and structural unit (IV) in the range which does not impair the effect of this invention. In addition, the [A] polymer may have 2 or more types of each structural unit.

[Structural unit (I)]
The structural unit (I) is a structural unit containing at least one selected from the group consisting of a group represented by the above formula (1) and a group represented by the above formula (2). [A] Since the polymer has the structural unit (I) and the structural unit (II) described later, the positive radiation-sensitive resin composition is excellent in storage stability while maintaining good surface hardness. In addition, it is possible to form a cured film that can sufficiently satisfy general characteristics such as sensitivity, development adhesion, heat resistance, chemical resistance, transmittance, and dielectric constant. This is because the hydroxyl group in the group represented by the formula (1) and / or (2) contained in the structural unit (I) and the cyclic ether and / or cyclic carbonate contained in the structural unit (II) described later are included. This is because the surface hardness of the cured film can be maintained by reacting and forming a strong cross-linked structure, and the above reaction is difficult to proceed at room temperature, so that thickening during storage is suppressed and good storage stability is obtained. It is assumed that there is.

In said formula (1), R < ¹ > and R < ² > are respectively independently a hydrogen atom, a C1-C4 alkyl group, or a C1-C4 fluorinated alkyl group. However, at least one of R ¹ and R ² is a fluorinated alkyl group having 1 to 4 carbon atoms.
In the above formula (2), ^{R 3} and ^{R 4} are each independently a hydrogen atom, a halogen atom, a fluorinated alkyl group of 1 to 4 alkyl groups or carbon atoms having 1 to 4 carbon atoms. However, at least one of R ³ and R ⁴ is a halogen atom or a fluorinated alkyl group having 1 to 4 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ^{1 to} R ⁴ include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec -A butyl group, a t-butyl group, etc. are mentioned.

The fluorinated alkyl group having 1 to 4 carbon atoms represented by R ^{1 to} R ⁴ is a group in which part or all of the hydrogen atoms of the alkyl group having 1 to 4 carbon atoms are substituted with fluorine atoms. Examples of the alkyl group having 1 to 4 carbon atoms, for example, can be applied same groups as the groups exemplified as the alkyl group having 1 to 4 carbon atoms represented by R ¹ to R ^4.

  As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.

As the ^R 1 to R ^4, a fluorinated alkyl group having 1 to 4 carbon atoms, a halogen atom. As said C1-C4 fluorinated alkyl group, a C1-C4 perfluoroalkyl group is more preferable, and a trifluoromethyl group is further more preferable. The halogen atom is more preferably a fluorine atom.

  As the structural unit (I) containing a group represented by the above formula (1), structural units represented by the following formulas (1a) and (1b) are preferable.

In the above formulas (1a) and (1b), each R is independently a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group or a trifluoromethyl group. R ¹ and R ² have the same meaning as in the above formula (1). R ⁵ and R ⁶ are each independently an (n + 1) -valent organic group. n is an integer of 1-5 each independently. When n is 2 or more, the plurality of R ¹ and R ² may be the same or different.

Examples of the (n + 1) -valent organic group represented by R ⁵ and R ⁶ include a chain (n + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and an (n + 1) -valent hydrocarbon group having 3 to 20 carbon atoms. An alicyclic hydrocarbon group, an (n + 1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms, a chain hydrocarbon group having 1 to 20 carbon atoms, or an alicyclic hydrocarbon having 3 to 20 carbon atoms (N + 1) valent group etc. which combined 2 or more types among group and C6-C20 aromatic hydrocarbon groups are mentioned. However, one part or all part of the hydrogen atom which these groups have may be substituted.

  Examples of the chain-like (n + 1) -valent hydrocarbon group having 1 to 20 carbon atoms include groups in which n hydrogen atoms have been removed from a linear or branched alkyl group having 1 to 20 carbon atoms. It is done.

  Examples of the linear or branched alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1- Examples thereof include a methylpropyl group and a t-butyl group.

  Examples of the (n + 1) -valent alicyclic hydrocarbon group having 3 to 20 carbon atoms include groups in which n hydrogen atoms have been removed from a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. It is done.

  Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

  Examples of the (n + 1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms include a group in which n hydrogen atoms have been removed from a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

  Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, and a naphthyl group.

Among these, as R ⁵ , a chain hydrocarbon group, an alicyclic hydrocarbon group, and a group obtained by combining these groups are preferable, and an ethylene group, a 1,2-propylene group, a 2,5-norbornylene group is preferable. A hydrocarbon group containing a 2,6-norbornylene group is more preferable. R ⁶ is preferably a divalent aromatic hydrocarbon group, more preferably a phenylene group.

  As the structural unit (I) containing a group represented by the above formula (2), structural units represented by the following formulas (2a) and (2b) are preferable.

In said formula (2a) and (2b), R is synonymous with said formula (1a) and (1b). R ³ and R ⁴ have the same meaning as in the above formula (2).

  Examples of the structural unit (I) include structural units represented by the following formulas (I-1) to (I-15).

  In said formula, R is synonymous with said formula (1a), (1b), (2a), and (2b). Among these, as the structural unit (I), structural units represented by the formulas (I-1) to (I-6), (I-9) and (I-11) to (I-13) are Preferably, from the viewpoints of alkali developability and thermosetting, structural units represented by formulas (I-1) to (I-6) are more preferable.

  The content ratio of the structural unit (I) is preferably 10 mol% or more and 90 mol% or less, more preferably 20 mol or more and 80 mol% or less, and more preferably 30 mol based on all the structural units constituting the [A] polymer. % To 70 mol% is more preferable. By making the content rate of structural unit (I) into the said range, storage stability etc. can be improved effectively.

[Structural unit (II)]
The structural unit (II) is a structural unit containing a cyclic ether structure or a cyclic carbonate structure.

  Examples of the cyclic ether structure include an oxirane structure (1,2-epoxy structure), an oxetane structure (1,3-epoxy structure), and a tetrahydrofuran structure.

As the structural unit (II), for example,
As a unit containing an oxirane structure, structural units represented by the following formulas (II-1) to (II-5);
As structural units containing an oxetane structure, structural units represented by the following formulas (II-6) to (II-9);
As a structure containing a tetrahydrofuran structure, structural units represented by the following formulas (II-10) and (II-11);
Examples of those containing a cyclic carbonate structure include structural units represented by the following formulas (II-12) to (II-16).

In the above formulas (II-1) to (II-16), R ⁷ is a hydrogen atom, a methyl group or a trifluoromethyl group. Among these, the structural unit (II) is represented by formulas (II-1) to (II-9) and (I-12) to (II-16) from the viewpoint of crosslinkability and chemical resistance. The structural units represented by formulas (II-1) to (II-9) are more preferred, and the structural units represented by formulas (II-1) to (II-5) are more preferred. The structural units represented by the formulas (II-1) to (II-3) are particularly preferable.

  The content ratio of the structural unit (II) is preferably 1 mol% or more and 70 mol% or less, more preferably 5 mol% or more and 50 mol% or less, with respect to all the structural units constituting the [A] polymer. More preferably, it is more than mol% and less than 30 mol%. By making the content rate of structural unit (II) into the said range, storage stability etc. can be improved effectively.

  The structural unit (II) includes a cyclic ether structure, and the cyclic ether structure is preferably at least one of an oxirane structure and an oxetane structure. When the structural unit (II) contains the structure, the crosslinkability can be improved. As a result, the positive radiation-sensitive resin composition can improve surface hardness, heat resistance, and the like.

[Structural unit (III)]
The structural unit (III) is a structural unit derived from a (meth) acrylic acid ester having a hydroxyl group or a structural unit derived from a compound represented by the following formula (3). [A] Since the polymer has the structural unit (III), it is possible to control alkali developability and suppress residues.

In said formula (3), R 'is a hydrogen atom or a C1-C4 alkyl group. R ^{L1 to} R ^L5 are each independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms. Y is a single bond, —COO—, or —CONH—. p is an integer of 0-3. However, at least one of R ^{L1 to} R ^L5 is a hydroxyl group.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ^{L1 to} R ^L5 include the same groups as those exemplified as the alkyl group having 1 to 4 carbon atoms represented by R ^{1 to} R ^4. Can be applied.

  Examples of the structural unit (III) include structural units represented by the following formulas (III-1) to (III-11).

In the above formulas (III-1) to (III-11), R ⁸ is a hydrogen atom, a methyl group, or a trifluoromethyl group. p is synonymous with the above formula (3). Among these, as the structural unit (III), structural units represented by the formulas (III-1), (III-4) and (III-10) are preferable.

  As the monomer compound giving the structural unit (III), 2-hydroxyethyl methacrylate, 4-hydroxyphenyl methacrylate, o-hydroxystyrene, p-hydroxystyrene, α-methyl-p-hydroxystyrene is preferable. Ethyl methacrylate, 4-hydroxyphenyl methacrylate, and α-methyl-p-hydroxystyrene are more preferable.

  The content ratio of the structural unit (III) is preferably 0 mol% or more and 50 mol% or less, more preferably 1 mol% or less and 30 mol% or less with respect to all the structural units constituting the [A] polymer. % 20 mol% or less is more preferable.

[Structural unit (IV)]
The structural unit (IV) is a structural unit other than the structural units (I) to (III). The structural unit (IV) is not particularly limited as long as it is a structural unit other than the structural units (I) to (III). [A] The polymer has a structural unit (IV), which adjusts the glass transition temperature of the resin and improves alkali developability, melt flow properties during thermal curing, mechanical strength of the cured film, and chemical resistance, respectively. can do.

  Examples of the structural unit (IV) include structural units represented by the following formulas (IV-1) to (IV-11).

In the above formulas (IV-1) to (IV-11), R ⁹ is a hydrogen atom, a methyl group, or a trifluoromethyl group. R ^M is a hydrogen atom or a methyl group. s is an integer of 1-10. Among these, as the structural unit (IV), structural units represented by the formulas (IV-1), (IV-2), (IV-7) to (IV-9), and (IV-11) are included. preferable.

  Examples of the monomer compound that gives the structural unit (IV) include (meth) acrylic acid, (meth) acrylic acid chain alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, Saturated dicarboxylic acid diester, bicyclounsaturated compound, maleimide compound, unsaturated aromatic compound and conjugated diene compound, and tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton, or a skeleton represented by the following formula (4) Examples thereof include structural units derived from saturated compounds and other unsaturated compounds.

In said formula (4), ^RM and s are synonymous with said formula (IV-1)-(IV-11).

  Examples of the (meth) acrylic acid chain alkyl ester include, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and isodecyl acrylate. Acrylic acid chain alkyl esters such as n-lauryl acrylate, tridecyl acrylate, n-stearyl acrylate; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate Methacrylic acid chain alkyl esters such as 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, and the like.

Examples of the (meth) acrylic acid cyclic alkyl ester include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, tricyclo [ 5.2.1.0 ^2,6 ] decan-8-yloxyethyl, acrylic acid cyclic alkyl ester such as isobornyl acrylate; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclomethacrylate [5.2.1 .0 ^2,6] decan-8-yl methacrylate tricyclo [5.2.1.0 ^2,6] decan-8-yl oxy ethyl, and methacrylic acid cyclic alkyl esters such as methacrylic acid isobornyl is.

  Examples of the (meth) acrylic acid aryl ester include phenyl acrylate. Examples include acrylic acid aryl esters such as benzyl acrylate; and aryl methacrylates such as phenyl methacrylate and benzyl methacrylate.

  Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate, and the like.

  Examples of the bicyclo unsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2. 1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2 2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene , 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (t-butoxycarbonyl) bicyclo [2.2.1] F To-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] hept-2 -Ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene and the like.

  Examples of the maleimide compound include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, and N-succinimidyl-3-maleimide. Examples include benzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, and N- (9-acridinyl) maleimide.

  Examples of the unsaturated aromatic compound include styrene, α-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, and the like.

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

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

  Examples of the unsaturated compound having a furan skeleton include 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3- En-2-one, 1-furan-2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan- 2-yl-hex-1-en-3-one, acrylic acid-2-furan-2-yl-1-methyl-ethyl ester, 6- (2-furyl) -6-methyl-1-heptene-3- ON etc. are mentioned.

  Examples of the unsaturated compound containing the tetrahydropyran skeleton include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1-ene-3. -One, 2-methacrylic acid tetrahydropyran-2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one and the like.

  Examples of the unsaturated compound having a pyran skeleton include 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyran, 4- (1,5-dioxa-6- Oxo-7-octenyl) -6-methyl-2-pyran and the like.

  Examples of the other unsaturated compounds include (meth) acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, and vinyl acetate.

Among these, as the monomer compound giving the structural unit (IV), methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, maleimide compound, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton, the above An unsaturated compound, an unsaturated aromatic compound, and an acrylic acid cyclic alkyl ester having a skeleton represented by the formula (4) are preferable. From the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution, styrene, methyl methacrylate, methacrylic acid are used. T-butyl acid, n-lauryl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N -Cyclohexyl maleimide, (meth) acrylic acid teto Tetrahydrofurfuryl, polyethylene glycol (n = 2 to 10) mono (meth) acrylate, 3- (meth) acryloyloxy-2-one is more preferred.

  The content ratio of the structural unit (IV) is preferably 0 mol% or more and 90 mol% or less, more preferably 1 mol% or more and 70 mol% or less, with respect to all the structural units constituting the [A] polymer. More preferably, it is more than mol% and less than 60 mol%. By making the content rate of structural unit (IV) into the said range, chemical-resistance can be improved effectively.

<[A] Polymer Synthesis Method>
[A] The polymer can be produced, for example, by polymerizing a monomer corresponding to each predetermined structural unit in a suitable solvent using a radical 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 Separately, a method of dropping a reaction solvent or a monomer-containing solution into a polymerization reaction, a plurality of types of solutions containing each monomer, and a solution containing a radical initiator, It is preferable to synthesize by a method such as a method of dropping it into a reaction solvent or a solution containing a monomer to cause a polymerization reaction.

  What is necessary is just to determine the reaction temperature in these methods suitably with initiator seed | species. Usually, it is 30 degreeC-180 degreeC, 40 degreeC-160 degreeC is preferable, and 50 degreeC-140 degreeC is more preferable. The dropping time varies depending on the reaction temperature, the type of initiator, the monomer to be reacted, etc., but is usually 30 minutes to 8 hours, preferably 45 minutes to 6 hours, and more preferably 1 hour to 5 hours. . Further, the total reaction time including the dropping time varies depending on the conditions similarly to the dropping time, but is usually 30 minutes to 8 hours, preferably 45 minutes to 7 hours, and more preferably 1 hour to 6 hours.

  Examples of the radical initiator used in the polymerization include azobisisobutyronitrile (AIBN), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2 -Cyclopropylpropionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylpropionitrile) and the like. These initiators may be used alone or in combination of two or more.

  The polymerization solvent is not limited as long as it is a solvent other than a solvent that inhibits polymerization (nitrobenzene having a polymerization inhibiting effect, mercapto compound having a chain transfer effect, etc.) and can dissolve the monomer. Examples of the polymerization solvent include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester / lactone solvents, nitrile solvents, and the like. These solvents may be used alone or in combination of two or more.

  The polymer obtained by the polymerization reaction is preferably recovered by a reprecipitation method. That is, after completion of the polymerization reaction, the polymer is recovered as a powder by introducing the polymerization solution into a reprecipitation solvent. As the reprecipitation solvent, alcohols or alkanes can be used alone or in admixture of two or more. In addition to the reprecipitation method, the polymer can be recovered by removing low-molecular components such as monomers and oligomers by a liquid separation operation, a column operation, an ultrafiltration operation, or the like.

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

  [A] The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer is not particularly limited, but is preferably 1,000 or more and 30,000 or less, more preferably 5,000 or more and 20,000 or less. More preferred. [A] By making Mw of a polymer into the said range, the sensitivity and developability of the said positive type radiation sensitive resin composition can be improved.

  [A] The ratio (Mw / Mn) of the polymer Mw and the number average molecular weight (Mn) in terms of polystyrene by GPC is preferably 1 or more and 3 or less, and more preferably 1.5 or more and 2.5 or less.

<[B] Acid generator>
[B] The acid generator generates an acid upon irradiation with radiation or heating. When the positive radiation sensitive resin composition contains the [B] acid generator, it has a positive radiation sensitive property in which the exposed portion of the radiation is removed in the development step, and heating in the subsequent heating step. The generated acid functions as a crosslinking catalyst and can promote a crosslinking reaction to form a cured film having high heat resistance and surface hardness. The inclusion form of the [B] acid generator in the positive radiation sensitive resin composition is a polymer as described later (hereinafter, this embodiment is also referred to as “[B] acid generator”). Both of these embodiments may be incorporated as part of the above. The radiation is a concept including visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams, and the like.

  [B] Examples of the acid generator include oxime sulfonate compounds, sulfonimide compounds, and quinonediazide compounds. In addition, you may use these [B] acid generators individually or in combination of 2 or more types.

  As said oxime sulfonate compound, the compound containing the oxime sulfonate group represented by following formula (5) is preferable.

In said formula (5), ^Ra is a C1-C20 alkyl group, a C3-C20 alicyclic group, or a C6-C20 aryl group. However, some or all of the hydrogen atoms of these alkyl groups, alicyclic groups, and aryl groups may be substituted with substituents.

Examples of the alkyl group having 1 to 20 carbon atoms represented by ^Ra include, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, and a sec-butyl group. , T-butyl group and the like. Among these, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable.

As ^a C3-C20 alicyclic group represented by said Ra, ^a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group etc. are mentioned, for example.

  As a substituent which the said alkyl group and alicyclic group may have, a C1-C10 alkoxy group, a C1-C10 alicyclic group, etc. are mentioned, for example.

  As a C1-C10 alkoxy group as said substituent, a methoxy group, an ethoxy group, etc. are mentioned, for example.

The alicyclic group having 1 to 10 carbon atoms as the substituent, for example, of the alicyclic group having 3 to 20 carbon atoms represented by R ^a, is applied to those having 1 to 10 carbon atoms be able to.

As ^a C6-C20 aryl group represented by said Ra, ^a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group etc. are mentioned, for example. Among these, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group and a naphthyl group are more preferable.

  Examples of the substituent that the aryl group may have include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen atom.

  Examples of the alkyl group having 1 to 5 carbon atoms as the substituent include a methyl group and an ethyl group.

  Examples of the alkoxy group having 1 to 5 carbon atoms as the substituent include a methoxy group and an ethoxy group.

  Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  As a compound containing the oxime sulfonate group represented by said Formula (5), the oxime sulfonate compound represented by following formula (5-1) and (5-2) is preferable.

In the formulas (5-1) and (5-2), R ^a has the same meaning as the formula (5). X is a C1-C5 alkyl group, a C1-C5 alkoxy group, or a halogen atom. m is an integer of 0-3. When m is 2 or 3, a plurality of X may be the same or different.

  As the alkyl group having 1 to 5 carbon atoms, the alkoxy group having 1 to 5 carbon atoms and the halogen atom represented by X, for example, the same groups as those exemplified as the substituent can be applied. . Among these, the alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and the alkoxy group is a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom is preferably a chlorine atom or a fluorine atom. M is preferably 0 or 1. In particular, in the above formula (5-1), a compound in which m is 1, X is a methyl group, and the substitution position of X is an ortho position is preferable.

  Examples of the oxime sulfonate compound represented by the above formula (5) include the following formulas (5-1-i) to (5-1-iv), and (5-2-i) and (5-2-ii). ) And the like.

  Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, and N- (2-trifluoromethylphenyl). Sulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide (trifluoromethanesulfonic acid-1,8-naphthalimide), N- (camphorsulfonyloxy) naphthyl dicarboxylimide, N- (4-methyl Phenylsulfonyloxy) naphthyl dicarboxylimide, N- (phenylsulfonyloxy) naphthyl dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) naphthyl dica Boxylimide, N- (4-fluorophenylsulfonyloxy) naphthyl dicarboxylimide, N- (pentafluoroethylsulfonyloxy) naphthyl dicarboxylimide, N- (heptafluoropropylsulfonyloxy) naphthyl dicarboxylimide, N- (nonafluoro) Butylsulfonyloxy) naphthyl dicarboxylimide, N- (ethylsulfonyloxy) naphthyl dicarboxylimide, N- (propylsulfonyloxy) naphthyl dicarboxylimide, N- (butylsulfonyloxy) naphthyl dicarboxylimide, N- (pentylsulfonyl) Oxy) naphthyl dicarboxylimide, N- (hexylsulfonyloxy) naphthyl dicarboxylimide, N- (heptylsulfonyloxy) naphthyl dical Kishiruimido, N- (octyl sulfonyloxy) naphthyl dicarboxyl imide, N- (nonyl sulfonyloxy) naphthyl dicarboxylic imide and the like.

  Examples of the quinonediazide compound include a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide or 1,2-naphthoquinonediazidesulfonic acid amide. Can be used.

  Examples of the mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother nucleus other than the mother nucleus.

As a specific example of the mother nucleus, for example,
As trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, etc .;
As tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3,4 2,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, etc .;
As pentahydroxybenzophenone, 2,3,4,2 ′, 6′-pentahydroxybenzophenone and the like;
As hexahydroxybenzophenone, 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone, etc .;
As (polyhydroxyphenyl) alkane, bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tris (p-hydroxyphenyl) Ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl-4- Hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl-4 -Hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6 , 7,5 ′, 6 ′, 7′-hexanol, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan and the like;
As other mother nucleus, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 1- [1- (3- {1- (4-hydroxy) Phenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6 -Dihydroxyphenyl) -1-methylethyl) benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene, and the like.

  Among these, as the mother nucleus, 2,3,4,4′-tetrahydroxybenzophenone, 1,1,1-tris (p-hydroxyphenyl) ethane, 4,4 ′-[1- [4- [ 1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol is preferred.

  As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable, 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-naphthoquinone diazide-5-sulfonic acid chloride. Are more preferable, and 1,2-naphthoquinonediazide-5-sulfonic acid chloride is more preferable.

  As the 1,2-naphthoquinonediazidosulfonic acid amide, 2,3,4-triaminobenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid amide is preferable.

  In the condensation reaction of the phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazidesulfonic acid halide, preferably 30 mol% based on the number of OH groups in the phenolic compound or alcoholic compound. 1,2-naphthoquinonediazide sulfonic acid halide corresponding to 85 mol% or less and more preferably 50 mol% or more and 70 mol% or less can be used. In addition, the said condensation reaction can be implemented by a well-known method.

  [B] The content of the acid generator is preferably 5 parts by mass or more and 100 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less, and 20 parts by mass with respect to 100 parts by mass of the polymer [A]. More preferred is 40 parts by mass or less. [B] By setting the content of the acid generator within the above range, the difference in solubility between the irradiated portion and the unirradiated portion in the alkaline aqueous solution serving as the developer is large, and as a result, the patterning performance is improved. Further, the chemical resistance of the obtained cured film is also good.

<[C] solvent>
As the [C] solvent, a solvent that uniformly dissolves the [A] polymer, [B] acid generator, and optional components contained as necessary, and does not react with each component is used. In addition, you may use a [C] solvent individually or in combination of 2 or more types.

  [C] Examples of the solvent include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, hydrocarbon solvents, and the like.

As the alcohol solvent, for example,
As monoalcohol solvents, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, tert-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec -Pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol Call, furfuryl alcohol, phenol, cyclohexanol, methyl cyclohexanol, 3,3,5-trimethyl cyclohexanol, benzyl alcohol, diacetone alcohol and the like;
As polyhydric alcohol solvents, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2 , 4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and the like;
As polyhydric alcohol partial ether solvents, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol Mono butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and the like.

  Examples of the ether solvent include diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran.

  Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl- Examples include n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4-pentanedione, acetonyl acetone, acetophenone, and the like.

  Examples of the amide solvent include N, N′-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethyl. Examples include acetamide, N-methylpropionamide, N-methylpyrrolidone and the like.

  Examples of the ester solvent include methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, aceto Ethyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene acetate Recall monoethyl ether, diethylene glycol mono-n-propyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate diacetate Propylene glycol monomethyl ether, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, Methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate And the like.

Examples of the hydrocarbon solvent include:
As aliphatic hydrocarbon solvents, n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane , Methylcyclohexane and the like;
As aromatic hydrocarbon solvents, benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene , N-amyl naphthalene and the like.

  [C] The solvent may contain a high-boiling solvent such as caproic acid, caprylic acid, ethylene carbonate, and propylene carbonate together with the above solvent.

<Other optional components>
Other optional components that may be contained in the positive radiation sensitive resin composition include, for example, [A] cyclic ether compounds other than the polymer (hereinafter also referred to as “compound X”), antioxidants, interfaces. Examples include activators and adhesion aids. In addition, the said positive type radiation sensitive resin composition may use said each component individually or in combination of 2 or more types.

[Compound X]
Compound X is a cyclic ether compound other than the [A] polymer, and specifically includes a thermally reactive group such as an oxiranyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure). It is a compound that has. When the positive radiation sensitive resin composition contains compound X, the heat resistance, surface hardness, and the like of the obtained cured film can be improved. Compound X is preferably a compound having two or more oxiranyl groups or oxetanyl groups in the molecule.

Examples of the compound X having two or more oxiranyl groups in the molecule include:
As bisphenol type diglycidyl ethers, 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 diglycidyl ether, etc. ;
As polyglycidyl ethers of polyhydric alcohol, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ether, etc .;
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.

As a commercial product of compound X having two or more oxiranyl groups in the molecule, for example,
As bisphenol A type epoxy resin, Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828 (above, made by Japan Epoxy Resin) and the like;
As bisphenol F type epoxy resin, Epicoat 807 (manufactured by Japan Epoxy Resin) and the like;
As a phenol novolac type epoxy resin, Epicoat 152, 154, 157S65 (above, made by Japan Epoxy Resin), EPPN201, 202 (above, made by Nippon Kayaku), etc .;
As cresol novolac type epoxy resin, EOCN102, 103S, 104S, 1020, 1025, 1027 (manufactured by Nippon Kayaku Co., Ltd.), Epicoat 180S75 (manufactured by Japan Epoxy Resin) and the like;
As a polyphenol type epoxy resin, Epicoat 1032H60, XY-4000 (made by Japan Epoxy Resin) and the like;
Cyclic aliphatic epoxy resins include CY-175, 177, 179, Araldite CY-182, 192, 184 (above, manufactured by Ciba Specialty Chemicals), ERL-4234, 4299, 4221, 4206 (above, U C.C), Shodyne 509 (Showa Denko), Epicron 200, 400 (above, Dainippon Ink), Epicoat 871, 872 (above Japan Epoxy Resin), ED-5661, 5562 (Celanese coating)
Examples of the aliphatic polyglycidyl ether include Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.) and Epiol TMP (manufactured by NOF Corporation).

  Examples of the compound X having two or more oxetanyl groups in the molecule include 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene and di [1-ethyl- (3-oxetanyl) methyl. ] Ether (alias: 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 -Oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3- Xetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanyl) Methyl) 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-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3- Til-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 can be mentioned.

  Among these, as the compound X having two or more oxetanyl groups in the molecule, di [1-ethyl- (3-oxetanyl) methyl] ether, 1,4-bis [(3-ethyl-3-oxetanyl) Methoxy) methyl] benzene is preferred.

  The content of the compound X is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 1 part by mass or more and 50 parts by mass or less, with respect to 100 parts by mass of the [A] polymer. The following is more preferable. By making content of compound X into the said range, a sensitivity, heat resistance, etc. can be improved.

[Antioxidant]
The antioxidant is a component capable of decomposing radicals generated by exposure or heating, or peroxide generated by oxidation, and preventing the bond breakage of the polymer molecules. As a result, the obtained cured film is prevented from oxidative deterioration over time, and for example, changes in the thickness of the cured film can be suppressed.

  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. In these, as an antioxidant, the compound which has a hindered phenol structure is preferable.

  Examples of the compound having a hindered phenol structure include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene bis [3- (3,5-dithione). -Tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tris- (3,5-di-t-butyl-4- Hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N′-hexane-1, 6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide), 3, ', 3', 5 ', 5'-hexa-tert-butyl-a, a', a '-(mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthio) Methyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate, hexa Methylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6-xylyl) methyl ] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3 , 5- Riazin-2-ylamine) phenol, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 2,6-di-t-butyl -4-cresol and the like.

  Examples of commercially available compounds having the hindered phenol structure include, for example, ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80. , AO-330 (above, manufactured by ADEKA), SumilizerGM, GS, MDP-S, BBM-S, WX-R, GA-80 (above, manufactured by Sumitomo Chemical), IRGANOX1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 1525L, 245, 259, 3114, 565, IRGAMOD295 (above, manufactured by BASF), Yoshinox BHT, BB, 2246G, 425, 250, 930, SS, TT, 917, 314 (above, API Corporation) ®-made emissions), and the like.

  Among these, as the compound having a hindered phenol structure, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2, More preferred are 4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and 2,6-di-t-butyl-4-cresol.

  As content of antioxidant, 0.001 mass part or more and 5 mass parts or less are preferable with respect to 100 mass parts of [A] polymers, and 0.01 mass part or more and 2 mass parts or less are more preferable.

[Surfactant]
The surfactant is a component that improves the film-forming property of the positive radiation-sensitive resin composition. Examples of the surfactant include a fluorine-based surfactant, a silicone-based surfactant, and other surfactants.

  The fluorine-based surfactant is preferably a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least one of the terminal, main chain and side chain, for example, 1,1,2,2-tetrafluoro- n-octyl (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, hexaethylene glycol di (1,1,2, , 2,3,3-hexafluoro-n-pentyl) ether, octaethylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di (1,1,2,2,3) , 3-Hexafluoro-n-pentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether Perfluoro-n-dodecane sodium sulfonate, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-decafluoro- n-dodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarboxylate, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkylammonium iodide, fluoroalkylbetaine, other fluoroalkylpolyesters Examples thereof include oxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, and carboxylic acid fluoroalkyl ester.

  Examples of commercially available fluorosurfactants include BM-1000, BM-1100 (manufactured by BM CHEMIE), MegaFuck F142D, F172, F173, F183, F178, F191, F191, and F471. , F476 (above, manufactured by Dainippon Ink and Chemicals), Florard FC-170C, -171, -430, -431 (above, manufactured by Sumitomo 3M), Surflon S-112, -113, -131 -141, -145, -382, Surflon SC-101, -102, -103, -104, -105, -106 (above, manufactured by Asahi Glass), F-top EF301, 303 352 (above, manufactured by Shin-Akita Kasei), FT-100, -110, -140A, -150, -250, 251, the -300, the -310, the -400S, FTX-218, the -251 (or, Neos Co., Ltd.) and the like.

  Examples of commercially available silicone surfactants include Toray Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, and SZ-6032. SF-8428, DC-57, DC-190 (made by Toray Dow Corning Silicone), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (Above, GE Toshiba Silicone), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

  Examples of the other surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene-n-octylphenyl ether, polyoxyethylene- Nonionic surfactants such as polyoxyethylene aryl ethers such as n-nonylphenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate.

  As a commercial item of the said other surfactant, (meth) acrylic acid type copolymer polyflow No. is mentioned, for example. 57, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

  As content of the said surfactant, 0.01 mass part or more and 3 mass parts or less are preferable with respect to 100 mass parts of [A] polymers, and 0.05 mass part or more and 1 mass part or less are more preferable. By making the content of the surfactant in the above range, the film formability can be effectively improved.

[Adhesion aid]
The adhesion assistant is a component that improves the adhesion between the obtained cured film and the substrate. As the adhesion assistant, a functional silane coupling agent having a reactive functional group such as a carboxy group, a methacryloyl group, a vinyl group, an isocyanate group, or an oxiranyl group is preferable.

  Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and γ-glycid. Examples include xylpropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

  As content of the said adhesion adjuvant, 0.01 mass part or more and 20 mass parts or less are preferable with respect to 100 mass parts of [A] polymers, and 0.1 mass part or more and 15 mass parts or less are more preferable. When the usage-amount of an adhesion assistant exceeds 20 mass parts, there exists a tendency for it to become easy to produce the image development remainder.

<Method for preparing positive-type radiation-sensitive resin composition>
The positive radiation-sensitive resin composition of the present invention comprises [A] polymer, [B] acid generator, and optionally [C] solvent, antioxidant, surfactant, adhesion aid and other optional components. Can be prepared by mixing at a predetermined ratio. The prepared positive radiation sensitive resin composition is preferably filtered with a filter having a pore size of about 0.5 μm, for example.

<Method for forming cured film>
The method for forming the cured film of the present invention is as follows.
(1) A step of forming a coating film on a substrate using the positive radiation sensitive resin composition,
(2) A step of irradiating a part of the coating film with radiation,
(3) a step of developing the coating film irradiated with the radiation; and (4) a step of heating the developed coating film.
Since the positive radiation sensitive resin composition has the above-mentioned properties, according to the method for forming a cured film of the present invention, it has good surface hardness, development adhesion, heat resistance, chemical resistance. Further, it is possible to form a cured film that can sufficiently satisfy general characteristics such as transmittance and relative dielectric constant. Hereinafter, each process is explained in full detail.

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

  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. Among these, the spin coating method, bar coating method, and slit die coating method are preferable as the coating method. The pre-baking conditions may vary depending on the type of each component, the usage ratio, and the like, but may be, for example, 60 ° C. to 130 ° C. for 30 seconds to 10 minutes. The film thickness of the coating film formed is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, and even more preferably 0.1 μm to 4 μm 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.

Examples of the ultraviolet rays include g-line (wavelength 436 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 to} 10,000 J / m ² .

[Step (3)]
In this step, the coating film irradiated with the radiation is developed. Specifically, the coating film irradiated with radiation in the step (2) is developed with a developer to remove the radiation irradiated portion. 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, Methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5- An aqueous solution of an alkali (basic compound) such as diazabicyclo [4,3,0] -5-nonane is exemplified. 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 that dissolve the positive-type radiation-sensitive resin composition is developed. It may be used as a liquid.

As a developing method, for example, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method, or the like can be employed. The development time varies depending on the composition of the positive radiation sensitive resin composition, but can be, for example, 30 seconds to 120 seconds. After the development step, the patterned coating film is rinsed with running water, and then exposed to a whole surface with a high-pressure mercury lamp or the like (post-exposure) to remain in the coating film [B It is preferable to perform a decomposition treatment of the acid generator. The exposure amount in this post-exposure is preferably 2,000 J / m ^{2 to} 5,000 J / m ² .

[Step (4)]
In this step, the developed coating film is heated. Specifically, the coating film is cured by heating and baking treatment (post-baking) of the coating film using a heating device such as a hot plate or an oven for baking the coating film developed in the step (3). . As a calcination temperature in this process, 200 degrees C or less is preferable. In addition to the ability to form a fine pattern using radiation sensitivity, the formation method can be used to form a cured film such as an interlayer insulating film on a plastic substrate of a flexible display by being capable of firing at such a low temperature. It can be preferably used. As baking temperature, 120 to 180 degreeC is more preferable, and 120 to 150 degreeC is further more preferable. The firing time varies depending on the type of heating equipment, but for example, 5 to 40 minutes when heat treatment is performed on a hot plate, and 30 to 80 minutes when heat treatment is performed in an oven. More preferably, it is within 30 minutes when heat treatment is performed on a hot plate, and within 60 minutes when heat treatment is performed in an oven. In this way, a patterned coating film corresponding to a target cured film such as an interlayer insulating film can be formed on the substrate.

<Curing film>
The cured film of the present invention is formed by using the positive radiation sensitive resin composition described above, for example, by the method for forming the cured film described above. Since the cured film is formed using the positive-type radiation-sensitive resin composition, it has a good surface hardness, such as development adhesion, heat resistance, chemical resistance, transmittance and relative dielectric constant. It is possible to fully satisfy the characteristics.

<Semiconductor element>
The semiconductor element of the present invention includes the cured film. Since the semiconductor element includes a cured film formed from the positive radiation-sensitive resin composition, the degree of circuit integration and recording density can be improved, and display elements, LEDs, solar cells, and other electronic devices It can be suitably used for a device.

<Display element>
The display element of the present invention includes the semiconductor element. This semiconductor element has a cured film formed from the positive radiation sensitive resin composition. This satisfies the general characteristics required for practical use as a display element. Examples of the display element include a liquid crystal display element. In the liquid crystal display element, for example, two TFT array substrates having a liquid crystal alignment film formed on the surface thereof are arranged opposite to each other on the liquid crystal alignment film side through a sealant provided at the periphery 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 such as an interlayer insulating film.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. The measuring method of each physical property value is shown below.

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

<[A] Synthesis of polymer>
The monomer compounds used in the synthesis of the polymers of Examples and Comparative Examples are shown below.

[Monomer compound giving structural unit (I)]
Monomer compounds (1-1) to (1-10) represented by the following formulas (1-1) to (1-10)

[Monomer compound giving structural unit (II)]
Monomer compounds (2-1) to (2-7) represented by the following formulas (2-1) to (2-7)

[Monomer compound giving structural unit (III)]
(3-1): p-hydroxyphenyl methacrylate (4-hydroxyphenyl methacrylate)
(3-2): Hydroxyethyl methacrylate (2-hydroxyethyl methacrylate)
(3-3): α-methyl-p-hydroxystyrene

[Monomer compound giving structural unit (IV)]
(4-1): Methacrylic acid (4-2): Styrene (4-3): Methyl methacrylate (4-4): N-cyclohexylmaleimide (4-5): Tetrahydrofurfuryl methacrylate (4-6) : Tricyclomethacrylate [5.2.1.0 ^2,6 ] decan-8-yl

[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 220 parts by mass of diethylene glycol methyl ethyl ether. Next, 60 parts by mass of the compound (1-1) giving the structural unit (I), 18 parts by mass of the compound (2-1) giving the structural unit (II), and the compound (4-2) 22 giving the structural unit (IV) Polymer containing copolymer (A-1) by charging mass part, substituting with nitrogen, gradually increasing the temperature of the solution to 70 ° C. while maintaining this temperature for 4 hours and polymerizing A solution was obtained. The solid content concentration of this polymer solution was 30.4% by mass, the Mw of the copolymer (A-1) was 8,000, and the molecular weight distribution (Mw / Mn) was 2.3.

[Synthesis Examples 2-45] (Synthesis of polymers (A-2) to (A-42) and (a-1) to (a-3))
Polymers (A-2) to (A-42) and (a-1) to (a-1) to (a) are used in the same manner as in Synthesis Example 1 except that the types and amounts of monomer compounds shown in Table 1 below are used. a-3) was synthesized. The solid content concentration of each polymer solution obtained, and the Mw and Mw / Mn of each polymer were equivalent to the value of the polymer (A-1). In addition, the blank in Table 1 shows that the corresponding monomer compound was not mix | blended.

<Preparation of positive radiation sensitive resin composition>
[B] acid generator used for preparation of each positive type radiation sensitive resin composition is shown below.

[B] Acid generator B-1: trifluoromethanesulfonic acid-1,8-naphthalimide B-2: 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl ] Condensation product of phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) B-3: 1,1,1-tri (p-hydroxy) Phenyl) ethane and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) condensate B-4: compound represented by the above formula (5-1-i)

[Example 1]
[A] A polymer solution containing 100 parts by mass (solid content) of (A-1) as a polymer, [B] 30 parts by mass of (B-2) as an acid generator, an adhesion assistant (γ-glyce Sidoxypropyltrimethoxysilane) 5 parts by mass, surfactant (FTX-218, manufactured by Neos) 0.5 part by mass, antioxidant (IRGANOX1010, manufactured by BASF) 0.1 part by mass, and solid content concentration After adding diethylene glycol methyl ethyl ether as the solvent [C] so that the amount of the positive electrode was 30% by mass, a positive radiation sensitive resin composition was prepared by filtering through a membrane filter having a pore size of 0.2 μm.

[Examples 2 to 58 and Comparative Examples 1 to 6]
Each positive radiation sensitive resin composition was prepared in the same manner as in Example 1 except that the [A] polymer and the [B] acid generator were changed to the types shown in Table 2.

<Evaluation>
Each prepared positive radiation sensitive resin composition was evaluated according to the following evaluation method. The evaluation results are shown in Table 2.

[Storage stability]
Each positive-type radiation sensitive resin composition was allowed to stand in an oven at 40 ° C. for 1 week, and the viscosity before and after heating was measured to determine the rate of change in viscosity (%), which was used as an index of storage stability. V: Viscosity change rate is less than 5%, B: Viscosity change rate is 5% or more and less than 10%, C: Viscosity change rate is 10 or more and less than 15%, D: Viscosity change rate is 15% or more, A or B In the case of, the storage stability was evaluated as good, and in the case of C or D, it was evaluated as poor. The viscosity was measured at 25 ° C. using an E-type viscometer (VISCONIC ELD.R, manufactured by Toki Sangyo).

[sensitivity]
Each positive radiation sensitive resin composition was applied on a silicon substrate using a spinner, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was irradiated with a predetermined amount of ultraviolet rays by a mercury lamp through a pattern mask having a line and space pattern having a width of 10 μm. Next, using a developer composed of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, development processing was carried out at 25 ° C. for 60 seconds, followed by washing with ultrapure water for 1 minute. At this time, the minimum ultraviolet irradiation amount capable of forming a line and space pattern having a width of 10 μm was measured. When this measured value is less than 500 J / m ² , the sensitivity is good, and when it is 500 J / m ² or more, it can be evaluated as defective.

[Development adhesion]
Each positive radiation sensitive resin composition was applied on a silicon substrate using a spinner, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was irradiated with 500 J / m ² of ultraviolet rays by a mercury lamp through a pattern mask having a line and space pattern having a width of 10 μm. Next, using a developer composed of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, development processing was carried out at 25 ° C. for 60 seconds, followed by washing with ultrapure water for 1 minute. Then, the presence or absence of peeling of the line and space pattern having a width of 10 μm was observed with a microscope to obtain development adhesion. At this time, depending on the presence or absence of peeling, A: no peeling, B: slight peeling, C: partial peeling, D: full peeling, and in the case of A or B, the development adhesion is good, C or D In the case of, it was evaluated as bad.

[chemical resistance]
Each positive radiation sensitive resin composition was applied on a silicon substrate using a spinner, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays with a mercury lamp so that the cumulative irradiation amount was 3,000 J / m ² . Next, this silicon substrate was heated on a hot plate at 200 ° C. for 30 minutes, and the thickness (T1) of the obtained cured film was measured. And after immersing the silicon substrate in which this cured film was formed in the dimethyl sulfoxide temperature-controlled at 70 degreeC for 20 minutes, the film thickness (t1) of the said cured film after the said immersion was measured, and film thickness change The rate was calculated from the following formula and used as an index of chemical resistance.
Film thickness change rate = {(t1-T1) / T1} × 100 (%)
When the absolute value of this value is less than 5%, the chemical resistance is good, and when it is 5% or more, it can be evaluated as defective.

[Heat-resistant]
Each positive radiation sensitive resin composition was applied on a silicon substrate using a spinner, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays with a mercury lamp so that the cumulative irradiation amount was 3,000 J / m ² . Next, this silicon substrate was heated on a hot plate at 200 ° C. for 30 minutes to obtain a cured film. The 5% thermal weight loss temperature of the obtained cured film was measured under air using a measuring instrument (TG / DTA220U, manufactured by SII Nanotechnology) and used as an index of heat resistance. At this time, when the 5% weight loss temperature is 300 ° C. or higher, the heat resistance is good, and when it is lower than 300 ° C., the heat resistance can be evaluated as poor.

[Transmissivity]
Each positive radiation sensitive resin composition was applied on a glass substrate using a spinner, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays with a mercury lamp so that the cumulative irradiation amount was 3,000 J / m ² . Next, this glass substrate was heated on a hot plate at 200 ° C. for 30 minutes to obtain a cured film. The transmittance of the obtained cured film was measured using an ultraviolet-visible spectrophotometer (V-630, manufactured by JASCO Corporation). At this time, a case where the transmittance of light having a wavelength of 400 nm is 95% or more can be evaluated as good (good transparency), and a case where it is less than 95% is evaluated as poor (poor transparency).

[surface hardness]
Each positive radiation sensitive resin composition was applied on a silicon substrate using a spinner, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays with a mercury lamp so that the cumulative irradiation amount was 3,000 J / m ² . Next, this silicon substrate was heated on a hot plate at 200 ° C. for 30 minutes to obtain a cured film. And about the board | substrate with which the cured film was formed, the pencil hardness of the cured film was measured by the 8.4.1 pencil scratch test of JISK-5400-1990, and this was made into the parameter | index of surface hardness. When the pencil hardness is 3H or higher, the surface hardness of the cured film is good (the positive radiation sensitive resin composition has sufficient curability), and when it is 2H or lower, it can be evaluated as defective.

[Relative permittivity]
Using a spinner, each positive radiation sensitive resin composition was applied on a SUS substrate, 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. Using an exposure machine (MPA-600FA, manufactured by Canon), the coating film is exposed so that the integrated dose becomes 9,000 J / m ^2, and the exposed substrate is heated at 200 ° C. for 30 minutes in a clean oven. As a result, a cured film was formed on the SUS substrate. Next, a Pt / Pd electrode pattern was formed on the cured film by vapor deposition to produce a dielectric constant measurement sample. For the substrate having this electrode pattern, the relative dielectric constant was measured by a CV method at a frequency of 10 kHz using an electrode (HP16451B, Yokogawa / Hewlett Packard) and a precision LCR meter (HP4284A, Yokogawa / Hewlett Packard). . At this time, it can be evaluated that the case where the relative dielectric constant is 3.9 or less is good and the case where the relative dielectric constant exceeds 3.9 is bad.

  In addition to excellent storage stability while maintaining good surface hardness, the present invention sufficiently satisfies general characteristics such as sensitivity, development adhesion, heat resistance, chemical resistance, transmittance, and dielectric constant. A positive-type radiation-sensitive resin composition capable of forming a cured film that can be formed can be provided. Accordingly, the positive radiation sensitive resin composition, a cured film formed from the positive radiation sensitive resin composition, a semiconductor element and a display element, and a method for forming the cured film include electronic devices such as flexible displays, etc. It can be suitably used in the manufacturing process.

Claims (5)

[A] Structural unit (I) containing at least one selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2), and a structural unit containing an oxetane structure ( II) and a positive radiation-sensitive resin composition containing [B] an acid generator.

(In Formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluorinated alkyl group having 1 to 4 carbon atoms, provided that R ¹ and R 2 are ^At least one of ² is a fluorinated alkyl group having 1 to 4 carbon atoms.
In Formula (2), R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluorinated alkyl group having 1 to 4 carbon atoms. However, at least one of R ³ and R ⁴ is a halogen atom or a fluorinated alkyl group having 1 to 4 carbon atoms. )   A cured film formed from the positive radiation-sensitive resin composition according to claim 1. (1) A step of forming a coating film on a substrate using the positive radiation sensitive resin composition according to claim 1;
(2) A step of irradiating a part of the coating film with radiation,
(3) The process of developing the coating film irradiated with the said radiation, (4) The formation method of the cured film which has the process of heating the said developed coating film.   A semiconductor element provided with the cured film of Claim 2.   A display element comprising the semiconductor element according to claim 4.