JP6089743B2 - Radiation-sensitive resin composition for forming cured film, cured film, method for forming the same, semiconductor element and display element - Google Patents

Description

  The present invention relates to a thermosetting resin composition for forming a cured film, a radiation-sensitive resin composition for forming a cured film, a cured film, 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, a cured film forming resin composition having excellent surface hardness and capable of forming a cured film that can sufficiently satisfy general properties such as chemical resistance, heat resistance, transmittance, and dielectric constant, and is excellent in storage stability. Things are sought.

JP 2001-354822 A

  The present invention has been made based on the circumstances as described above, and its purpose is to have excellent surface hardness and sufficiently satisfy general characteristics such as chemical resistance, heat resistance, transmittance, and dielectric constant. An object of the present invention is to provide a resin composition for forming a cured film that can form a cured film that is possible and that is excellent in storage stability.

（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のうちのいずれかは、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のうちのいずれかは、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] 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 crosslinkable group (a1) A cured film-forming thermosetting resin composition (hereinafter referred to as “cured film-forming resin composition”) comprising a polymer having a structural unit (II-1) containing (hereinafter also referred to as “[A1] polymer”). (Also referred to as “(1)”).

(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 Any one of ² is a C1-C4 fluorinated alkyl group.
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, 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:
(1) Using the cured film-forming resin composition (1), a step of forming a coating film on a substrate, and (2) a method of forming a cured film, which includes a step of heating the coating film (hereinafter referred to as “curing” Film formation method (1) ").

（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のうちのいずれかは、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のうちのいずれかは、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。） Moreover, another invention made in order to solve the said subject is:
[A] 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 crosslinkable group (a2) A polymer having a structural unit (II-2) containing (hereinafter, also referred to as “[A2] polymer”),
[B] A polymerizable compound having an ethylenically unsaturated bond (hereinafter also referred to as “[B] polymerizable compound”), and [C] a radiation-sensitive resin composition for forming a cured film containing a radiation-sensitive polymerization initiator (Hereinafter also referred to as “cured film forming resin composition (2)”).

(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 Any one of ² is a C1-C4 fluorinated alkyl group.
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, 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:
(1) The process of forming a coating film on a board | substrate using the said resin composition for cured film formation (2),
(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 method of forming a cured film comprising a step of heating the developed coating film (hereinafter referred to as “cured film forming method (2)”). It is also called).

Furthermore, another invention made to solve the above problems is
A cured film formed from the cured film-forming resin composition (1) (hereinafter also referred to as “cured film (1)”),
A cured film formed from the cured film-forming resin composition (2) (hereinafter also referred to as “cured film (2)”),
A semiconductor element including the cured film; and a display element including the semiconductor element.

  The “crosslinkable group” refers to a group that can form a covalent bond between the same or different molecules.

  The present invention is for forming a cured film having excellent surface hardness and capable of forming a cured film sufficiently satisfying general characteristics such as chemical resistance, heat resistance, transmittance and relative dielectric constant, and excellent in storage stability. A resin composition can be provided. Accordingly, the cured film-forming resin composition, the cured film formed from the cured film-forming resin composition, the semiconductor element and the display element, and the method of forming the cured film are used for manufacturing electronic devices such as flexible displays. It can be suitably used for the process.

<Resin composition for forming cured film (1)>
The cured film forming resin composition (1) of the present invention contains [A1] polymer. Moreover, the said resin composition for cured film formation (1) may contain other components other than a [A1] polymer in the range which does not impair the effect of this invention.

  Since the cured film-forming resin composition (1) contains the [A1] polymer, it is a so-called thermosetting resin composition that is cured by crosslinking by heating. Hereinafter, each component will be described in detail.

<[A1] Polymer>
[A1] The polymer is a polymer having the structural unit (I) and the structural unit (II-1). [A1] The polymer may have the structural unit (III) and the structural unit (IV) as long as the effects of the present invention are not impaired. [A1] Since the polymer has the structural unit (I) and the structural unit (II-1), the cured film-forming resin composition (1) has excellent surface hardness and chemical resistance and heat resistance. In addition, a cured film that can sufficiently satisfy general characteristics such as transmittance and relative dielectric constant can be formed, and storage stability is excellent. This is because during heating, the hydroxyl group in the group represented by the formula (1) and / or (2) contained in the structural unit (I) and the crosslinkable group (a1) contained in the structural unit (II-1). ) And the formation of a strong cross-linked structure makes it possible to obtain an excellent surface hardness of the cured film, and the reaction is difficult to proceed at room temperature. As a result, thickening during storage is suppressed and good storage is achieved. It is assumed that this is because stability is obtained. In addition, the [A1] 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).

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, either R ¹ or 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, 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 fluorinated alkyl group having 1 to 4 carbon atoms represented by R ^{1 to} R ⁴ include a difluoromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, and 2,2,2-trifluoro. Ethyl group, perfluoroethyl group, 2,2,3,3-tetrafluoropropyl group, perfluoroethylmethyl group, perfluoropropyl group, 2,2,3,3,4,4-hexafluorobutyl group, perfluoropropyl group Examples include a fluorobutyl group and a 1,1-dimethyl-2,2,3,3-tetrafluoropropyl group. Of these, the fluorinated alkyl group having 1 to 4 carbon atoms is preferably a trifluoromethyl group.

Examples of the halogen atom represented by R ³ and R ⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, the halogen atom is 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 (n + 1) -valent chain hydrocarbon groups having 1 to 20 carbon atoms and (n + 1) -valent fats having 3 to 20 carbon atoms. A cyclic 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, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and (N + 1) valent group etc. which combined 2 or more types of 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 (n + 1) -valent chain hydrocarbon group having 1 to 20 carbon atoms include a group in which n hydrogen atoms have been removed from a linear or branched alkyl group having 1 to 20 carbon atoms. .

  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.

As R ⁵ , a methylene group, an ethylene group, a 1,3-propylene group or a 1,2-propylene group or other propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, Nonamethylene group, Decamemethylene group, Undecamethylene group, Dodecamethylene group, Tridecamethylene group, Tetradecamethylene group, Pentadecamethylene group, Hexadecamethylene group, Heptadecamethylene group, Octadecamethylene group, Nonadecamethylene group, Insalene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, 2-methyl-1,2-propylene group, 1-methyl-1,4-butylene group, 2-methyl -1,4-butylene group, methylidene group, ethylidene group, propylidene group, 2-propylidene group, etc. Saturated chain hydrocarbon group; cyclobutylene group such as 1,3-cyclobutylene group, cyclopentylene group such as 1,3-cyclopentylene group, cyclohexylene group such as 1,4-cyclohexylene group, 1, Monocyclic hydrocarbon ring groups such as cycloalkylene groups such as cyclooctylene groups such as 5-cyclooctylene groups; norbornylene groups such as 1,4-norbornylene groups or 2,5-norbornylene groups, 1,5-adamans A polycyclic hydrocarbon group such as a thylene group or an adamantylene group such as a 2,6-adamantylene group, a cyclohexanetriyl group such as a 1,3,5-cyclohexanetriyl group; An aromatic hydrocarbon group such as a 4-phenylene group or a group obtained by combining these groups is preferable, and an ethylene group, a 1,2-propylene group, Norbornylene group, a 1,4-phenylene group, 1,3,5-cyclohexane tricarboxylic yl group is more preferable. R ⁶ is preferably a divalent aromatic hydrocarbon group such as a 1,3-phenylene group or a 1,4-phenylene group, and more preferably a 1,4-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 viewpoint of 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 [A1] 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-1)]
The structural unit (II-1) is a structural unit containing a crosslinkable group (a1).

  Examples of the crosslinkable group (a1) include an oxiranyl group (1,2-epoxy structure), an oxetanyl group (1,3-epoxy structure), a cyclic carbonate group, and a (meth) acryloyl group.

Examples of the building unit (II-1) containing an oxiranyl group include structural units represented by the following formulas (II-1) to (II-5).
Examples of the building unit (II-1) containing an oxetanyl group include structural units represented by the following formulas (II-6) to (II-9).
Examples of the building unit (II-1) containing a cyclic carbonate group include structural units represented by the following formulas (II-10) to (II-14).

In the above formulas (II-1) to (II-14), R ⁷ is a hydrogen atom, a methyl group or a trifluoromethyl group.

  Examples of the structural unit (II-1) containing a (meth) acryloyl group include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and propylene glycol di (meth). ) Acrylate, dipropylene di (meth) acrylate, tripropylene di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) ) Di (meth) acrylate compounds such as acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol diacrylate; tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylo Tri (meth) acrylate compounds such as lepropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate; tetra (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate; penta (such as dipentaerythritol penta (meth) acrylate) Examples include structural units derived from monomeric compounds such as (meth) acrylate compounds.

  Among these, the crosslinkable group (a1) is preferably at least one selected from the group consisting of an oxiranyl group and an oxetanyl group. Thereby, the chemical resistance of the cured film formed can be improved more.

  The content ratio of the structural unit (II-1) is preferably 1 mol% or more and 70 mol% or less, and more preferably 5 mol% or more and 50 mol% or less with respect to all the structural units constituting the [A1] polymer. 10 mol% or more and 30 mol% or less are more preferable. By making the content rate of structural unit (II-1) into the said range, storage stability etc. can be improved effectively.

[Structural unit (III)]
[A1] The polymer may have a structural unit (III) described later. As a content rate of structural unit (III), it can determine suitably in the range which does not impair the effect of this invention.

[Structural unit (IV)]
[A1] The polymer may have a structural unit (IV) described later. [A1] Since the polymer has the structural unit (IV), the cured film-forming resin composition (1) adjusts the glass transition temperature of the resin, and the melt flow property during thermal curing and the cured film obtained The mechanical strength and chemical resistance can be improved.

  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, based on all the structural units constituting the [A1] 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.

<[A1] Polymer Synthesis Method>
[A1] 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 can be recovered by a reprecipitation method. That is, after completion of the polymerization reaction, the polymer is recovered as a powder by putting the polymer 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. In addition, when the polymerization solvent is the same as the solvent of the cured film-forming resin composition (1) prepared, a cured film can be obtained by using the obtained polymer solution as it is or by adding a solvent to the obtained polymer solution. You may use for preparation of the resin composition for formation (1).

  [A1] 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.

  [A1] 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. The ratio (Mw / Mn) of [A1] polymer Mw to polystyrene-reduced number average molecular weight (Mn) by GPC is preferably 1 or more and 3 or less, and more preferably 1.5 or more and 2.5 or less.

<Other ingredients>
Other components that may be contained in the cured film forming resin composition (1) include, for example, [D] antioxidant, [E] surfactant, and [F] adhesion assistant in addition to the solvent described below. Agents and the like. In addition, the said resin composition for cured film formation (1) may use said each component individually or in combination of 2 or more types.

<[D] Antioxidant>
[D] 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.

  [D] 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 a [D] 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.

  [D] The content of the antioxidant is preferably 0.001 part by mass or more and 5 parts by mass or less, and more preferably 0.01 part by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the polymer [A1]. . [D] By making content of antioxidant into the said range, the oxidative deterioration with time of the cured film obtained can be prevented effectively.

<[E] surfactant>
[E] Surfactant is a component that improves film-forming properties. [E] 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- Examples thereof include polyoxyethylene aryl ethers such as n-nonylphenyl ether; nonionic surfactants such as 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.).

  [E] The content of the surfactant is preferably 0.01 parts by mass or more and 3 parts by mass or less, and more preferably 0.05 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass of the polymer [A1]. . [E] By making the content of the surfactant within the above range, the film forming property can be effectively improved.

<[F] Adhesion aid>
[F] The adhesion assistant is a component that improves the adhesion between the obtained cured film and the substrate. [F] 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.

  [F] The content of the adhesion assistant is preferably 0.01 parts by mass or more and 20 parts by mass or less, and more preferably 0.1 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the polymer [A1]. .

<Method for Preparing Resin Composition (1) for Forming Cured Film>
The resin composition (1) for forming a cured film of the present invention can be prepared by mixing the [A1] polymer and other components as required in a predetermined ratio, and preferably dissolving in a suitable solvent. The prepared cured film-forming resin composition (1) is preferably filtered, for example, with a filter having a pore diameter of about 0.2 μm.

  As a solvent used for the preparation of the cured film forming resin composition (1), each component contained in the cured film forming resin composition (1) is uniformly dissolved or dispersed and does not react with the above components. Things are used. Examples of such solvents 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.

  The solvent may further contain a high boiling point solvent such as caproic acid, caprylic acid, ethylene carbonate, propylene carbonate.

<Method for forming cured film (1)>
The method (1) for forming a cured film of the present invention comprises:
(1) A step of forming a coating film on a substrate using the cured film-forming resin composition (1) (hereinafter also referred to as “step (A1)”), and (2) a step of heating the coating film (Hereinafter also referred to as “step (A2)”)
Have
Since the cured film-forming resin composition (1) has the above properties, according to the cured film forming method (1) of the present invention, heat resistance, chemical resistance, transmittance, relative dielectric constant, etc. It is possible to form a cured film sufficiently satisfying the general characteristics of and having excellent surface hardness. Hereinafter, each process is explained in full detail.

[Step (A1)]
In this step, a coating film is formed on the substrate using the cured film-forming resin composition (1). Specifically, the solution of the cured film forming resin composition (1) is applied to the surface of the substrate, and preferably, pre-baking is performed to remove the solvent and form a coating film. Examples of the substrate include a glass substrate, a silicon substrate, a plastic substrate, and a substrate on which various metal thin films are formed. Examples of the plastic substrate include 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 use 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 (A2)]
In this step, the coating film is cured by heating. Although it does not specifically limit as a heating method, For example, it can heat using heating apparatuses, such as oven and a hotplate. The heating temperature in this step is preferably 200 ° C. or lower. Since the heating at such a low temperature is possible, the method (1) for forming the cured film can be suitably used for forming a cured film such as an interlayer insulating film on a plastic substrate of a flexible display. As heating temperature, 120 to 180 degreeC is more preferable, and 120 to 150 degreeC is further more preferable. The heating 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 desired cured film (1) such as an interlayer insulating film can be formed on the substrate.

<Curing film (1)>
The cured film (1) of the present invention is formed from the cured film-forming resin composition (1). Although it does not specifically limit as a formation method of the said cured film (1), Preferably it can form using the above-mentioned formation method (1) of the said cured film. Since the cured film (1) is formed from the cured film-forming resin composition (1), it has excellent surface hardness and general chemical resistance, heat resistance, transmittance, dielectric constant, and the like. The characteristics can be fully satisfied. Since the said cured film (1) has the said characteristic, it is suitable, for example as an interlayer insulation film of a display element, a spacer, a protective film, a coloring pattern for color filters, etc.

<Resin composition for forming a cured film (2)>
The cured film forming resin composition (2) of the present invention contains a [A2] polymer, a [B] polymerizable compound and a [C] radiation sensitive polymerization initiator. Moreover, the said resin composition (2) for cured film formation may contain [D] antioxidant as a suitable component. Furthermore, the said resin composition for cured film formation (2) may contain other arbitrary components other than the [A] component-[D] component in the range which does not impair the effect of this invention.

  Since the cured film-forming resin composition (2) contains the [A2] polymer, the [B] polymerizable compound, and the [C] radiation sensitive polymerization initiator, the portion irradiated with radiation (exposure) Part) is cured by polymerization, and a part other than the above exposed part (unexposed part) is dissolved and removed by development with an alkali developer so that a pattern can be formed. It is. Therefore, the cured film-forming resin composition (2) can form a patterned cured film. Hereinafter, each component will be described in detail.

<[A2] Polymer>
[A2] The polymer is a polymer having the structural unit (I) and the structural unit (II-2). [A2] The polymer may have the structural unit (III) and the structural unit (IV) as long as the effects of the present invention are not impaired. [A2] The polymer has the structural unit (I) and the structural unit (II-2), so that the cured film-forming resin composition (2) is similar to the cured film-forming resin composition (1). ) Can form a cured film having excellent surface hardness and sufficiently satisfying general characteristics such as chemical resistance, heat resistance, transmittance, and dielectric constant, and is excellent in storage stability. In addition, the cured film-forming resin composition (2) includes an alcoholic hydroxyl group easily desorbed by an electron-withdrawing property of the fluorinated alkyl group represented by the formula (1), and the formula (2). It exhibits acidity due to the easy elimination of the hydrogen atom of the phenolic hydroxyl group due to the electron withdrawing property of the halogen atom and / or fluorinated alkyl group represented by the formula, and as a result, the development residue due to the alkaline developer in the unexposed area is reduced. can do. In addition, the [A2] 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).

  Since this structural unit (I) is the same as the structural unit (I) in the above-mentioned [A1] polymer, its detailed description is omitted.

  The content ratio of the structural unit (I) is preferably 5 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 [A2] 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-2)]
The structural unit (II-2) is a structural unit containing a crosslinkable group (a2).

  As the structural unit (II-2), for example, the same structural unit as the structural unit exemplified in the above structural unit (II-1) and the like can be mentioned.

  The crosslinkable group (a2) is preferably at least one selected from the group consisting of an oxiranyl group, an oxetanyl group, a cyclic carbonate group, and a (meth) acryloyl group. Thereby, the chemical resistance of the cured film formed can be improved more.

  As a content rate of structural unit (II-2), 1 mol% or more and 70 mol% or less are preferable with respect to all the structural units which comprise a [A2] polymer, and 5 mol% or more and 50 mol% or less are more preferable. 10 mol% or more and 30 mol% or less are more preferable. By making the content rate of structural unit (II-2) into the said range, storage stability etc. can be improved effectively.

[Structural unit (III)]
The structural unit (III) is a structural unit other than the structural unit (I), and 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). is there. [A2] When 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, a methyl group, or a trifluoromethyl 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 [A2] 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). [A2] When the polymer has the structural unit (IV), the cured film-forming resin composition (2) adjusts the glass transition temperature of the resin, and develops alkali developability, melt flow property during thermosetting, The mechanical strength and chemical resistance of the cured film can be improved.

  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, and unsaturated. Unsaturation having dicarboxylic acid diester, bicyclo unsaturated compound, maleimide compound, unsaturated aromatic compound and conjugated diene compound, and tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton or skeleton represented by the following formula (4) Examples thereof include structural units derived from 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-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, α-methyl-p-hydroxystyrene, 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 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one, and tetrahydrofurfuryl (meth) acrylate. .

  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 unsaturated compound having a skeleton represented by the above formula (4) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and propylene glycol di (meth). Examples include acrylate, dipropylene glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate.

  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 having a skeleton represented by the formula (4), an unsaturated aromatic compound, and a cyclic alkyl ester of acrylic acid are preferable, and styrene, methacrylic acid, methacrylic acid from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution. Methyl, t-butyl methacrylate, n-lauryl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenyl Maleimide, N-cyclohexylmaleimide, (meth) Acrylic acid 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, based on all the structural units constituting the [A2] 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.

<[A2] Polymer Synthesis Method>
[A2] The method for synthesizing the polymer is not particularly limited, and for example, the same method as the method for synthesizing the above [A1] polymer can be applied.

  [A2] The polystyrene-reduced weight average molecular weight (Mw) by gel permeation chromatography (GPC) of the polymer is preferably 1,000 or more and 30,000 or less, and more preferably 5,000 or more and 20,000 or less. [A2] By making Mw of a polymer into the said range, the sensitivity and developability of the said resin composition for cured film formation (2) can be improved more. Further, the ratio (Mw / Mn) of [A2] polymer Mw to polystyrene-reduced number average molecular weight (Mn) by GPC is preferably 1 or more and 3 or less, and more preferably 1.5 or more and 2.5 or less.

<[B] Polymerizable compound>
[B] The polymerizable compound is a compound having an ethylenically unsaturated bond. In addition, you may use [B] polymeric compound individually or in combination of 2 or more types.

  [B] The polymerizable compound is not particularly limited as long as it is a polymerizable compound having an ethylenically unsaturated bond. For example, ω-carboxypolycaprolactone mono (meth) acrylate, 2- (2′-vinyloxyethoxy) Monofunctional (meth) acrylate compounds such as ethyl (meth) acrylate; ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol Di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenoxyethanol full orange (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, 2-hydroxy-3- (Meth) acryloyloxypropyl methacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Tri (2- (meth) acryloyloxyethyl) phosphate, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid modified pentaerythritol triacrylate, linear alkylene group and alicyclic structure, and two or more A urethane obtained by reacting a compound having an isocyanate group with a compound having one or more hydroxyl groups and 3 to 5 (meth) acryloyloxy groups in the molecule ( Examples include polyfunctional (meth) acrylate compounds such as (meth) acrylate compounds.

[B] Examples of commercially available polymerizable compounds include:
Aronix M-400, M-402, M-405, M-450, M-1310, M-1600, M-1960, M-7100, M-8030, M-8060, M-8100, M-8530, M-8560, M-9560, M-9050, Aronix TO-1450, TO-1382 (above, manufactured by Toagosei);
KAYARAD DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, MAX-3510 (manufactured by Nippon Kayaku);
Biscote 295, 300, 360, GPT, 3PA, 400 (above, manufactured by Osaka Organic Chemical Industry);
As a urethane acrylate compound, New Frontier R-1150 (Daiichi Kogyo Seiyaku);
KAYARAD DPHA-40H, UX-5000 (above, manufactured by Nippon Kayaku);
UN-9000H (Negami Kogyo);
Aronix M-5300, M-5600, M-5700, M-210, M-220, M-240, M-270, M-6200, M-305, M-309, M M-310, M-315 (above, manufactured by Toagosei);
KAYARAD HDDA, KAYARAD HX-220, HX-620, R-526, R-167, R-604, R-684, R-551, R-712, UX-2201, UX-2301 UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937, MU-2100, MU-4001 (above, manufactured by Nippon Kayaku);
Art Resin UN-9000PEP, UN-9200A, UN-7600, UN-333, UN-1003, UN-1255, UN-6060PTM, UN-6060P (manufactured by Negami Kogyo);
SH-500B biscoat 260, 312 and 335HP (above, manufactured by Osaka Organic Chemical Industry) and the like.

  [B] The polymerizable compound preferably has at least one carboxy group in the same molecule. Thereby, the improvement of a crosslinkability and the reduction | decrease of the image development residue in an unexposed part can be aimed at. As the [B] polymerizable compound having at least one carboxy group in the same molecule, ω-carboxypolycaprolactone mono (meth) acrylate and succinic acid-modified pentaerythritol triacrylate are preferable.

  [B] The content of the polymerizable compound is preferably 20 parts by mass or more and 200 parts by mass or less, and more preferably 40 parts by mass or more and 160 parts by mass or less with respect to 100 parts by mass of the [A] polymer. [B] By setting the content of the polymerizable compound in the above range, the cured film-forming resin composition (2) is a cured film having excellent adhesion and sufficient surface hardness even at a low exposure amount. Can be formed.

<[C] Radiation sensitive polymerization initiator>
[C] The radiation-sensitive polymerization initiator is a component that generates an active species capable of initiating polymerization of the [B] polymerizable compound in response to radiation. [C] Examples of the radiation-sensitive polymerization initiator include oxime ester compounds, acetophenone compounds, biimidazole compounds, and the like. In addition, you may use [C] radiation sensitive polymerization initiators individually or in combination of 2 or more types.

  Examples of the oxime ester compound include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1,2-octane. Dione-1- [4- (phenylthio) -2- (O-benzoyloxime)], 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -octane-1-oneoxime-O-acetate 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2- Ethylbenzoyl) -9H-carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-teto) Hydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9H- Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] O-acyloxime compounds such as -1- (O-acetyloxime) and the like can be mentioned. Among these, oxime ester compounds include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1,2 -Octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazole -3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl}- 9H-carbazol-3-yl] -1- (O-acetyloxime) is preferred.

  Examples of the acetophenone compound include an α-aminoketone compound and an α-hydroxyketone compound.

  Examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and the like can be mentioned.

  Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane-1- ON, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone and the like.

  The acetophenone compound is preferably an α-aminoketone compound, such as 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2- More preferred is methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 ′ -Biimidazole etc. are mentioned. Among these, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) ) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'- Tetraphenyl-1,2′-biimidazole is preferred, and 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole is more preferred. .

  [C] Examples of commercially available radiation-sensitive polymerization initiators include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Irgacure 907), 2-dimethylamino-2. -(4-Methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (Irgacure 379), 1,2-octanedione-1- [4- (phenylthio) -2 -(O-benzoyloxime)] (Irgacure OXE01), ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure) OXE02) (manufactured by Ciba Specialty Chemicals).

  [C] The content of the radiation sensitive polymerization initiator is preferably 0.1 parts by mass or more and 40 parts by mass or less, and 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polymer [A]. Is more preferable. [C] By setting the content of the radiation sensitive polymerization initiator in the above range, the cured film-forming resin composition (2) has a cured film having sufficient surface hardness and adhesion even in the case of a low exposure amount. Can be formed.

  Furthermore, [C] the radiation sensitive polymerization initiator is an oxime ester compound, and the content of this oxime ester compound is 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the [A] polymer. Is preferably 1 part by mass or more and 5 parts by mass or less. Thereby, even in the case of a low exposure amount, a cured film having sufficient surface hardness and adhesion can be efficiently formed.

<[D] Antioxidant>
[D] 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. [D] As the antioxidant, the antioxidant described in the above section <Resin composition for forming a cured film (1)> can be applied. The cured film-forming resin composition (2) contains [D] an antioxidant, whereby the obtained cured film is prevented from oxidative deterioration over time, and suppresses, for example, a change in the thickness of the cured film. be able to. In addition, you may use [D] antioxidant individually or in combination of 2 or more types.

  [D] The content of the antioxidant is preferably 0 parts by mass or more and 5 parts by mass or less, and more preferably 0.01 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the polymer [A2]. [D] By making content of antioxidant into the said range, the oxidative deterioration with time of the cured film obtained can be prevented effectively.

<Other optional components>
Examples of other optional components that may be contained in the cured film-forming resin composition (2) include [E] surfactants and [F] adhesion aids in addition to solvents. In addition, about each other arbitrary component, what was demonstrated by the term of the above-mentioned <resin composition for cured film formation (1)> is applicable.

<Method for Preparing Cured Film Forming Resin Composition (2)>
The resin composition (2) for forming a cured film of the present invention can be prepared by mixing the [A2] polymer and other components as required in a predetermined ratio, and preferably dissolving in a suitable solvent. Examples of the solvent used for the preparation of the cured film forming resin composition (2) include the same solvents as those exemplified in the above section <Preparation method of the cured film forming resin composition (1)>. Can be applied. The prepared cured film-forming resin composition (2) is preferably filtered, for example, with a filter having a pore diameter of about 0.2 μm.

<Method for forming cured film (2)>
The method (2) for forming the cured film of the present invention comprises:
(1) A step of forming a coating film on a substrate using the cured film-forming resin composition (2) (hereinafter also referred to as “step (B1)”),
(2) A step of irradiating a part of the coating film with radiation (hereinafter also referred to as “step (B2)”),
(3) a step of developing the coating film irradiated with the radiation (hereinafter also referred to as “step (B3)”), and (4) a step of heating the developed coating film (hereinafter referred to as “step (B4)”). Is also called)
Have
Since the cured film-forming resin composition (2) has the above properties, according to the cured film forming method (2) of the present invention, heat resistance, chemical resistance, transmittance, relative dielectric constant, etc. It is possible to form a cured film sufficiently satisfying the general characteristics of and having excellent surface hardness. Hereinafter, each process is explained in full detail.

[Step (B1)]
In this step, a coating film is formed on the substrate using the cured film-forming resin composition (2). Specifically, the solution of the cured film forming resin composition (2) is applied to the substrate surface, and preferably a prebake is performed to remove the solvent and form a coating film. Examples of the substrate include a glass substrate, a silicon 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 (B2)]
In this step, a part of the coating film is irradiated with radiation. Specifically, the coating film formed in the step (B1) 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 (B3)]
In this step, the coating film irradiated with the radiation is developed. Specifically, the coating film irradiated with radiation in the step (B2) is developed with a developer to remove the radiation irradiated part. 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. Further, an alkali solution containing a small amount of various organic solvents capable of dissolving the aqueous resin solution or surfactant obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkali aqueous solution or the cured film forming resin composition (2) An aqueous solution may be used as a developer.

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 cured film forming resin composition (2), 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 irradiated with a high-pressure mercury lamp or the like on the entire surface (post-exposure) to remain in the coating film [C It is preferable to perform a decomposition treatment of the radiation sensitive polymerization initiator. The exposure amount in this post-exposure is preferably 2,000 J / m ^{2 to} 5,000 J / m ² .

[Step (B4)]
In this step, the developed coating film is heated. Specifically, the coating film is cured by heating (post-baking) the coating film using a heating device such as a hot plate or an oven for heating the coating film developed in the step (B3). The heating temperature in this step is preferably 200 ° C. or lower. In addition to the ability to form a fine pattern using radiation sensitivity, the method (2) for forming the cured film can provide interlayer insulation on a plastic substrate of a flexible display by enabling heating at such a low temperature. It can be suitably used for forming a cured film such as a film. As heating temperature, 120 to 180 degreeC is more preferable, and 120 to 150 degreeC is further more preferable. The heating 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 (2)>
The cured film (2) of the present invention is formed from the cured film-forming resin composition (2). Although it does not specifically limit as a formation method of the said cured film (2), Preferably it can form using the above-mentioned formation method (2) of the said cured film. Since the cured film (2) is formed from the cured film-forming resin composition (2), the cured film (2) has general surface hardness and chemical resistance, heat resistance, transmittance, dielectric constant, and the like. The characteristics can be fully satisfied. Since the said cured film (2) has the said characteristic, it is suitable as an interlayer insulation film of a display element, a spacer, a protective film, the coloring pattern for color filters, etc., for example.

<Semiconductor element>
The semiconductor element of the present invention includes the cured film (the cured film (1) or the cured film (2) described above). This cured film is used as, for example, an interlayer insulating film that insulates between wirings in the semiconductor element. The semiconductor element can be formed using a known method. Since the said semiconductor element is equipped with the said cured film, it can be used suitably for electronic devices, such as a display element, LED, and a solar cell.

<Display element>
The display element of the present invention includes the semiconductor element. Since the display element includes a semiconductor element having the cured film, the display element satisfies 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 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% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene

<Synthesis of [A1] polymer and [A2] 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-1) and structural unit (II-2)]
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-hydroxyphenol 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 monomer compound (1-1) giving the structural unit (I), 18 parts by mass of the monomer compound (2-1) giving the structural unit (II-1), and the structural unit (IV) The monomer compound (4-2) to be fed is charged with 22 parts by mass, purged with nitrogen, slowly stirred, and the temperature of the solution is raised to 70 ° C., and this temperature is maintained for 4 hours to polymerize. A polymer solution containing (A-1) was obtained. The polymer solution had a solid content concentration of 30.4%, and the polymer (A-1) had an Mw of 8,000 and a molecular weight distribution (Mw / Mn) of 2.3.

[Synthesis Examples 2-46] (Synthesis of Polymers (A-2) to (A-42) and (a-1) to (a-4))
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 monomer compounds having the types and blending amounts shown in Table 1 below are used. a-4) 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 cured film forming resin composition (1)>
[Example 1]
[A1] After adding diethylene glycol methyl ethyl ether as a solvent to a polymer solution containing 100 parts by mass (solid content) of (A-1) as a polymer so that the solid content concentration is 30% by mass, The resin composition for forming a cured film (1) was prepared by filtering through a membrane filter having a pore diameter of 0.2 μm.

[Example 2 and Comparative Example 1]
[A] Except having changed into the kind and compounding quantity which are shown in Table 2, it operated similarly to Example 1 and prepared each resin composition (1) for cured film formation. In addition, “-” in Table 2 indicates that the corresponding component was not blended or evaluation described later was not performed.

<Preparation of cured film forming resin composition (2)>
[B] polymerizable compound, [C] radiation sensitive polymerization initiator and [D] antioxidant used for the preparation of each cured film forming resin composition (2) are shown below.

[[B] polymerizable compound]
B-1: Dipentaerythritol hexaacrylate B-2: Mixture of polyfunctional acrylate compounds (KAYARAD DPHA-40H, manufactured by Nippon Kayaku Co., Ltd.)
B-3: 1,9-nonanediol diacrylate B-4: ω-carboxy-polycaprolactone monoacrylate (Aronix M-5300 (manufactured by Toagosei)
B-5: Succinic acid-modified pentaerythritol triacrylate

[[C] Radiation sensitive polymerization initiator]
C-1: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02, manufactured by Ciba Specialty Chemicals) )
C-2: 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] (Irgacure OXE01, manufactured by Ciba Specialty Chemicals)
C-3: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Irgacure 907, manufactured by Ciba Specialty Chemicals)
C-4: 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (Irgacure 379, manufactured by Ciba Specialty Chemicals)

[[D] Antioxidant]
D-1: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], (Adeka Stab AO-60, manufactured by ADEKA)
D-2: Tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate (ADK STAB AO-20, manufactured by ADEKA)

[Example 3]
[A2] A polymer solution containing 100 parts by mass (solid content) of (A-1) as a polymer, 50 parts by mass of (B-1) as a polymerizable compound, and [C] radiation sensitive After mixing 5 parts by mass of (C-1) as a polymerization initiator and further adding diethylene glycol methyl ethyl ether as a solvent so that the solid content concentration becomes 30% by mass, the mixture is filtered through a membrane filter having a pore size of 0.2 μm. By doing so, the resin composition (2) for cured film formation was prepared.

[Examples 4 to 50 and Comparative Examples 2 to 5]
The same operation as in Example 3 except that [A] component, [B] polymerizable compound, [C] radiation sensitive polymerization initiator, and [D] antioxidant were changed to the types and amounts shown in Table 2. Each cured film forming resin composition (2) was prepared. In addition, “-” in Table 2 indicates that the corresponding component was not blended.

<Evaluation>
Each prepared cured film-forming resin composition (1) and (2) was evaluated according to the following evaluation method. The evaluation results are shown in Table 2.

[Storage stability]
Each cured film forming 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]
Using a spinner, each cured film forming resin composition was applied onto a silicon substrate 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 700 J / m ² , the sensitivity is good, and when it is 700 J / m ² or more, it can be evaluated as defective.

[Development adhesion]
Using a spinner, each cured film forming resin composition was applied onto a silicon substrate 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 of 1,000 J / m ² 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 degree 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]
Using a spinner, each cured film forming resin composition was applied onto a silicon substrate 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 by a mercury lamp so that the cumulative irradiation amount was 1,000 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]
Using a spinner, each cured film forming resin composition was applied onto a silicon substrate 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 by a mercury lamp so that the cumulative irradiation amount was 1,000 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]
Using a spinner, each cured film forming resin composition was applied on a glass 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. The obtained coating film was irradiated with ultraviolet rays by a mercury lamp so that the cumulative irradiation amount was 1,000 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]
Using a spinner, each cured film forming resin composition was applied onto a silicon substrate 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 by a mercury lamp so that the cumulative irradiation amount was 1,000 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 more, the surface hardness of the cured film is good (the resin composition for forming a cured film has sufficient curability), and when it is 2H or less, it can be evaluated as defective.

[Relative permittivity]
Using a spinner, each cured film forming 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 irradiation amount becomes 1,000 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.

  As can be seen from the evaluation results in Table 2, in the examples, all the characteristics were good, while in the comparative example, any of the characteristics was bad.

  The present invention is for forming a cured film having excellent surface hardness and capable of forming a cured film sufficiently satisfying general characteristics such as chemical resistance, heat resistance, transmittance and relative dielectric constant, and excellent in storage stability. A resin composition can be provided. Accordingly, the cured film-forming resin composition, the cured film formed from the cured film-forming resin composition, the semiconductor element and the display element, and the method of forming the cured film are used for manufacturing electronic devices such as flexible displays. It can be suitably used for the process.

Claims (9)

[A] 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 crosslinkable group (a2) A polymer having a structural unit (II-2) containing,
[B] a polymerizable compound having an ethylenically unsaturated bond, and [C] a radiation-sensitive polymerization initiator ,
[C] A radiation-sensitive resin composition for forming a cured film , wherein the radiation-sensitive polymerization initiator is an oxime ester compound .

(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 Any one of ² is a C1-C4 fluorinated alkyl group.
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, one of R ³ and R ⁴ is a halogen atom or a fluorinated alkyl group having 1 to 4 carbon atoms. ) The radiation-sensitive resin for forming a cured film according to claim 1 , wherein the crosslinkable group (a2) is at least one selected from the group consisting of an oxiranyl group, an oxetanyl group, a cyclic carbonate group, and a (meth) acryloyl group. Composition. The content of the oxime ester compounds [A] Polymer 100 parts by weight cured film-forming radiation-sensitive resin composition according to claim 1 or claim 2 or less 10 parts by mass or more 0.1 part by mass with respect to object. [D] according to claim 1 which further comprises an antioxidant, cured film-forming radiation-sensitive resin composition according to claim 2 or claim 3. [B] the polymerizable compound, the cured film-forming radiation-sensitive resin composition as claimed in any one of claims 4 having at least one carboxyl group in the same molecule. (1) using the cured film forming radiation sensitive resin composition according to any one of claims 1 to 5, wherein the step of forming a coating on a substrate,
(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. The cured film formed from the radiation sensitive resin composition for cured film formation of any one of Claims 1-5 . A semiconductor element provided with the cured film of Claim 7 . A display element comprising the semiconductor element according to claim 8 .