KR20140145963A - Thermosetting resin composition for forming cured film, negative radiation-sensitive resin composition, positive radiation-sensitive resin composition, cured film, method for forming the same, semiconductor device and display device - Google Patents

Abstract

According to the present invention, a cured film, which has excellent hardness of the surface and has descent common properties such as sensitivity, development tightness, chemical resistance, heat resistance, transmittance, and a relative dielectric constant, can be formed. The present invention aims to provide: a thermosetting resin composition for forming a cured film having excellent storage stability; a negative radiation-sensitive resin composition; and a positive radiation-sensitive resin composition. The resin composition for forming a cured film includes a copolymer. The copolymer includes: a structure unit (I) including at least one selected from the group consisting of a group represented by chemical formula (1) and a group represented by chemical formula (2); and a structure unit including a cross-linking group (a1) represented by chemical formula (2).

Description

TECHNICAL FIELD [0001] The present invention relates to a thermosetting resin composition for forming a cured film, a negative radiation-sensitive resin composition, a positive radiation-sensitive resin composition, a cured film, COMPOSITION, POSITIVE RADIATION-SENSITIVE RESIN COMPOSITION, CURED FILM, METHOD FOR FORMING THE SAME, SEMICONDUCTOR DEVICE AND DISPLAY DEVICE}

The present invention relates to a thermosetting resin composition for forming a cured film, a negative radiation-sensitive resin composition, a positive radiation-sensitive resin composition, a cured film, a method of forming the same, a semiconductor device and a display device.

2. Description of the Related Art In recent years, a plastic substrate such as a polyethylene terephthalate or the like has been studied as a substrate for a flexible display, with attention being paid to a flexible display such as an electronic paper. Since the substrate undergoes elongation or shrinkage upon heating, the lowering of the temperature of the production process is under investigation, and in particular, the lowering of the firing temperature in the process of forming a cured film such as an interlayer insulating film which becomes the highest temperature in the manufacturing process is required.

As the material of the cured film capable of such a low temperature, a radiation-sensitive resin composition in which the number of processes at the time of pattern formation is small and high surface hardness is obtained is used, and for example, a radiation- sensitive resin composition containing a copolymer containing a carboxyl group and an epoxy group And the surface hardness of the cured film is obtained by reacting the carboxyl group and the epoxy group (see Japanese Patent Application Laid-Open No. 2001-354822).

However, in the radiation-sensitive resin composition containing the copolymer described above, there is a fear that the carboxyl group and the epoxy group react with each other even when the radiation-sensitive resin composition is stored, and as a result, the storage stability is lowered.

Therefore, it is possible to form a cured film which has satisfactory surface hardness and which can sufficiently satisfy general characteristics such as sensitivity, developing adhesion, chemical resistance, heat resistance, transmittance and relative dielectric constant, and is excellent in curing film forming resin A negative radiation-sensitive resin composition, and a positive radiation-sensitive resin composition.

Japanese Patent Laid-Open No. 2001-354822

The object of the present invention is to provide a cured film which has excellent surface hardness and can sufficiently satisfy general characteristics such as sensitivity, developing adhesion, chemical resistance, heat resistance, transmittance and relative dielectric constant A negative radiation-sensitive resin composition, and a positive radiation-sensitive resin composition, which are excellent in storage stability and can be formed.

In order to solve the above problems,

[A1] A resin composition comprising a structural unit (I) comprising at least one member selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2) (Hereinafter also referred to as "cured film-forming resin composition (1)") containing a polymer having a unit (II-1)

(In the 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 at least one of R ¹ and R ² has 1 to 4 carbon atoms Of fluorinated alkyl groups,

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, provided that at least one of R ³ and R ⁴ is a halogen atom Or a fluorinated alkyl group having 1 to 4 carbon atoms)

According to another aspect of the present invention,

(1) a step of forming a coating film on the substrate by using the resin composition (1) for forming a cured film, and

(2) a step of heating the coating film

(Hereinafter also referred to as "cured film forming method (1)").

According to another aspect of the present invention,

[A2] A resin composition comprising a structural unit (I) comprising at least one member selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2) The polymer having the unit (II-2) (hereinafter also referred to as the "[A2] polymer"),

[B] a polymerizable compound having an ethylenically unsaturated bond (hereinafter also referred to as "[B] polymerizable compound"), and

[C] Radiation-sensitive polymerization initiator

(Hereinafter also referred to as "negative-tone radiation-sensitive resin composition (2)").

(In the 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 at least one of R ¹ and R ² has 1 to 4 carbon atoms Of fluorinated alkyl groups,

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, provided that at least one of R ³ and R ⁴ is a halogen atom Or a fluorinated alkyl group having 1 to 4 carbon atoms)

According to another aspect of the present invention,

(1) a step of forming a coating film on the substrate by using the negative radiation-sensitive resin composition (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 step of heating the developed coating film

(Hereinafter also referred to as "cured film forming method (2)").

According to another aspect of the present invention,

(Hereinafter also referred to as "cured film (1)") formed from the resin composition for forming a cured film (1)

(Hereinafter also referred to as "cured film (2)") formed from the negative radiation-sensitive resin composition (2)

A semiconductor element having the cured film, and

The display element having the semiconductor element

.

The term "crosslinkable group" refers to a group capable of forming a covalent bond between the same or different molecules.

According to another aspect of the present invention,

[A3] A polymer comprising a structural unit (I) comprising at least one member selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2), and a cyclic ether structure or a cyclic carbonate structure , A polymer having a structural unit (II-3) (hereinafter, also referred to as "[A3] polymer"), and

[G] acid generator

Sensitive resin composition.

(In the 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 at least one of R ¹ and R ² has 1 to 4 carbon atoms Of fluorinated alkyl groups.

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, provided that at least one of R ³ and R ⁴ is a halogen atom Or a fluorinated alkyl group having 1 to 4 carbon atoms)

According to another aspect of the present invention,

(Hereinafter also referred to as "cured film 3") formed from the above positive radiation-sensitive resin composition,

A semiconductor element having the cured film, and

The display element having the semiconductor element

.

According to another aspect of the present invention,

(1) a step of forming a coating film on a substrate using the positive radiation-sensitive resin composition,

(2) a step of irradiating a part of the coating film with radiation,

(3) a step of developing the coating film irradiated with the radiation, and

(4) a step of heating the developed coating film

(Hereinafter also referred to as "cured film forming method (3)").

The present invention can provide a cured film which has excellent surface hardness and can sufficiently satisfy general characteristics such as sensitivity, developing adhesion, chemical resistance, heat resistance, transmittance and relative dielectric constant, A thermosetting resin composition, a negative-tone radiation-sensitive resin composition, and a positive-tone radiation-sensitive resin composition. Therefore, it is possible to provide a thermosetting resin composition for forming a cured film, a negative radiation-sensitive resin composition, a positive radiation-sensitive resin composition, a thermosetting resin composition for forming the cured film, a negative radiation- The cured film, the semiconductor element, the display element, and the method of forming the cured film formed from the composition can be suitably used in a manufacturing process of an electronic device such as a flexible display.

≪ Cured film-forming resin composition (1) >

The resin composition (1) for forming a cured film of the present invention contains a [A1] polymer. The resin composition for forming a cured film (1) may contain other components in addition to the polymer [A1], so long as the effect of the present invention is not impaired.

The cured film-forming resin composition (1) is a so-called thermosetting resin composition which is cured by crosslinking by heating because it contains the [A1] polymer. Each component will be described in detail below.

<[A1] Polymer>

[A1] The polymer is a polymer having the structural unit (I) and the structural unit (II-1). Further, the [A1] polymer may have the structural unit (III) and the structural unit (IV) within the range not to impair the effect of the present invention. By having the structural unit (I) and the structural unit (II-1) in the polymer [A1], the resin composition for forming a cured film (1) has excellent surface hardness and excellent resistance to chemicals, heat resistance, transmittance, The cured film can be sufficiently satisfied with the general characteristics of the film, and the storage stability is excellent. This is because the hydroxyl groups in the groups represented by the formulas (1) and / or (2) contained in the structural unit (I) and the crosslinkable group (a1) contained in the structural unit (II- , The cured film can obtain excellent surface hardness due to the formation of a strong crosslinked structure and at the same time the reaction is difficult to proceed at room temperature and the thickening is suppressed during storage and good storage stability is obtained . Further, the [A1] polymer may have two or more kinds of structural units.

[Structural unit (I)]

The structural unit (I) is a structural unit comprising at least one kind selected from the group consisting of the group represented by the above-mentioned formula (1) and the group represented by the above-mentioned formula (2).

In the above 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 at least one of R ¹ and R ² is a fluorinated alkyl group having 1 to 4 carbon atoms.

In the 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. Provided that at least one of R ³ and R ⁴ is a halogen atom or a fluorinated alkyl group having 1 to 4 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹ to R ⁴ include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i- -Butyl group and the like.

The fluorinated alkyl group having 1 to 4 carbon atoms represented by R ¹ to R ⁴ is a group in which a part or all of the hydrogen atoms contained in the alkyl group having 1 to 4 carbon atoms is substituted with a fluorine atom. Examples of the fluorinated alkyl group having 1 to 4 carbon atoms represented by R ¹ to R ⁴ include a fluoromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group , A perfluoroethyl group, a 2,2,3,3-tetrafluoropropyl group, a perfluoroethylmethyl group, a perfluoropropyl group, a 2,2,3,3,4,4-hexafluorobutyl group, A perfluorobutyl 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 are as defined in the above formula (1). R ⁵ and R ⁶ are each independently (n + 1) -valent organic groups. n is independently an integer of 1 to 5; When n is 2 or more, a plurality of R ¹ and R ² may be the same or different from each other.

R ⁵ and as the monovalent organic group (n + 1) represented by R ^6, for example having 1 to 20 carbon atoms in the (n + 1) valent chain hydrocarbon group, having 3 to 20 (n + 1) valent alicyclic hydrocarbon (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 an aromatic hydrocarbon group having 6 to 20 carbon atoms (N + 1) -valent groups obtained by combining the above-mentioned groups. However, some or all of the hydrogen atoms of these groups may be substituted.

Examples of the (n + 1) th chain hydrocarbon group having 1 to 20 carbon atoms include groups obtained by removing n hydrogen atoms from a linear or branched alkyl group having 1 to 20 carbon atoms.

Examples of the straight-chain or branched alkyl group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, -Butyl group and the like.

Examples of the (n + 1) -valent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a group obtained by removing n hydrogen atoms from a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms.

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 obtained by removing n hydrogen atoms 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.

Examples of R ⁵ include a propylene group such as a methylene group, an ethylene group, a 1,3-propylene group or a 1,2-propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, A methylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, a tridecamethylene group, a tetradecamethylene group, a pentadecamethylene group, a hexadecamethylene group, an heptadecamethylene group, an octadecamethylene group, Methylene-1,3-propylene group, 2-methyl-1,2-propylene group, 1-methyl-1,4-butylene group, 2 Saturated hydrocarbon groups such as methyl-1,4-butylene group, methylidene group, ethylidene group, propylidene group and 2-propylidene group; Cyclobutylene group such as 1,3-cyclobutylene group and the like, cyclopentylene group such as 1,3-cyclopentylene group and the like, cyclohexylene group such as 1,4-cyclohexylene group and 1,5-cyclooctylene group Monocyclic hydrocarbon ring group such as cycloalkylene group such as cyclooctylene group; A norbornylene group such as a 1,4-norbornylene group, a 2,5-norbornylene group or a 2,6-norbornylene group, a 1,5-adamantylene group or a 2,6-adamantylene group , Cyclohexanetriyl groups such as 1,3,5-cyclohexanetriyl group, and other polycyclic hydrocarbon groups such as cyclohexanetriyl group; An aromatic hydrocarbon group such as a 1,3-phenylene group or a 1,4-phenylene group, or a combination thereof is preferable, and an ethylene group, a 1,2-propylene group, a 2,5-norbornylene group, A phenylene group and a 1,3,5-cyclohexanetriyl group are more preferable. As R ⁶ , a bivalent aromatic hydrocarbon group such as a 1,3-phenylene group or a 1,4-phenylene group is preferable, and a 1,4-phenylene group is more preferable.

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

In the above formulas (2a) and (2b), R is as defined in the above formulas (1a) and (1b). R ³ and R ⁴ are as defined 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 the above formulas, R is synonymous with the above formulas (1a), (1b), (2a) and (2b). Among them, the structural unit (I) is preferably a structural unit represented by any of formulas (I-1) to (I-6), (I-9) and (I-11) to (I- (I-1) to (I-6) are more preferred from the viewpoints of adhesion, heat resistance and / or thermosetting property.

The content of the structural unit (I) is preferably from 10 to 90 mol%, more preferably from 20 to 80 mol%, and still more preferably from 30 to 30 mol%, based on the total structural units constituting the polymer (A1) Or more and 70 mol% or less. When the content ratio of the structural unit (I) is within the above range, storage stability and the like can be effectively improved.

[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. have.

Examples of the structural unit (II-1) containing an oxiranyl group include structural units represented by the following formulas (II-1) to (II-5).

Examples of the structural unit (II-1) containing an oxetanyl group include structural units represented by the following formulas (II-6) to (II-9).

Examples of the structural unit (II-1) containing a cyclic carbonate group include structural units represented by the following formulas (II-10) to (II-14).

In the 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 Propylene glycol di (meth) acrylate, dipropylene di (meth) acrylate, tripropylene di (meth) acrylate, 1,3-butylene glycol di Di (meth) acrylate compounds such as 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate and tripropylene glycol diacrylate; Tri (meth) acrylate compounds such as tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate; Tetra (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate; And a penta (meth) acrylate compound such as dipentaerythritol penta (meth) acrylate.

Among them, the crosslinkable group (a1) is preferably at least one selected from the group consisting of an oxiranyl group and an oxetanyl group. Thus, the chemical resistance of the formed cured film can be further enhanced.

The content of the structural unit (II-1) is preferably from 1 mol% to 70 mol%, more preferably from 5 mol% to 50 mol%, and still more preferably from 10 mol% to 10 mol%, based on the total structural units constituting the [A1] Mol% or more and 30 mol% or less. When the content ratio of the structural unit (II-1) is within the above range, storage stability and the like can be effectively improved.

[Structural unit (III)]

[A1] The polymer may have a structural unit (III) described later. The content of the structural unit (III) can be suitably determined within a range that does not impair the effect of the present invention.

[Structural unit (IV)]

[A1] The polymer may have the structural unit (IV) described later. By having the structural unit (IV) of the polymer [A1], the resin composition for forming a cured film (1) can be prepared by adjusting the glass transition temperature of the resin and controlling the melt flow during thermal curing, Strength and chemical resistance can be improved.

The content of the structural unit (IV) is preferably from 0 mol% to 90 mol%, more preferably from 1 mol% to 70 mol%, still more preferably from 3 mol% to 70 mol% based on the total structural units constituting the [A1] Or more and 60 mol% or less. By setting the content ratio of the structural unit (IV) within the above range, the chemical resistance can be effectively improved.

<Method of synthesizing [A1] polymer>

The [A1] polymer can be produced by, for example, polymerizing a monomer corresponding to a given structural unit in a suitable solvent using a radical initiator. For example, a method in which a solution containing a monomer and a radical initiator is added dropwise to a solution containing a reaction solvent or a monomer to effect polymerization, a solution containing a monomer, and a solution containing a radical initiator, A method in which a solution containing a monomer and a solution containing a radical initiator are separately added dropwise into a reaction solvent or a solution containing a monomer to effect polymerization reaction And the like.

The reaction temperature in these methods may be appropriately determined depending on the initiator species. But it is usually 30 to 180 ° C, preferably 40 to 160 ° C, and more preferably 50 to 140 ° C. The dropping time is usually from 30 minutes to 8 hours, preferably from 45 minutes to 6 hours, more preferably from 1 hour to 5 hours, although it depends on the conditions such as the reaction temperature, the kind of the initiator and the monomer to be reacted. The total reaction time including the dropping time also varies depending on the conditions like the dropping time, but is usually from 30 minutes to 8 hours, preferably from 45 minutes to 7 hours, more preferably from 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) and 2,2'-azobis (2-methylpropionitrile). 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 the polymerization inhibiting solvent (nitrobenzene having polymerization inhibiting effect, mercapto compound having chain transfer effect, etc.), and a solvent in which the monomer is soluble. Examples of the polymerization solvent include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester · lactone solvents and nitrile solvents. These solvents may be used alone or in combination of two or more.

The polymer obtained by the polymerization reaction can be recovered by the reprecipitation method. That is, after completion of the polymerization reaction, the polymer solution is put into a re-precipitation solvent to recover the objective polymer as a powder. As the re-precipitation solvent, alcohols, alkanes, etc. may be used alone or in combination of two or more. In addition to the reprecipitation method, a polymer may 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. When the polymerization solvent is the same as the solvent of the cured film-forming resin composition (1), the obtained polymer solution is used as it is or a solvent is added to the obtained polymer solution to prepare the cured film-forming resin composition (1) As shown in FIG.

In the polymerization reaction for producing the [A1] polymer, a molecular weight adjuster may be used to adjust the molecular weight. Examples of the molecular weight regulator include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexylmercaptan, n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan and thioglycolic acid; Xanthogens such as dimethylxanthogen sulfide and diisopropylxanthogen disulfide; Terpinolene,? -Methylstyrene dimer, and the like.

The polystyrene reduced weight average molecular weight (Mw) of the [A1] polymer by gel permeation chromatography (GPC) is not particularly limited, but is preferably 1,000 or more and 30,000 or less, and more preferably 5,000 or more and 20,000 or less. The ratio (Mw / Mn) of the Mw of the polymer [A1] to the polystyrene reduced number average molecular weight (Mn) by GPC is preferably 1 or more and 3 or less, more preferably 1.5 or more and 2.5 or less.

&Lt; Other components >

Examples of other components that may be contained in the resin composition for forming a cured film (1) include [D] an antioxidant, an [E] surfactant, and an [F] . The curable film-forming resin composition (1) may be used alone or in combination of two or more.

<[D] Antioxidant>

[D] The antioxidant is a component capable of decomposing a radical generated by exposure or heating, or a peroxide generated by oxidation, and preventing the cleavage of polymer molecules. As a result, the obtained cured film is prevented from deterioration with time of oxidation, and for example, the change in film 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. Among them, the [D] antioxidant is preferably a compound having a hindered phenol structure.

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-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5- -Hydroxybenzyl) benzene, N, N'-hexane-1,6-diylbis [3- (3,5- , 5 ', 5'-hexa-tert-butyl-a, a', a'- (mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylene bis (oxyethylene) bis [3- (5-tert- butyl-4-hydroxy-m- tolyl) propionate , Hexamethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris [ Methyl-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -triene, 2,6- Bis (octylthio) -1,3,5-triazin-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 products of the hindered phenol structure include Adekastab AO-20, AO-30, AO-40, AO-50, AO-60, AO- 80, AO-330 (manufactured by ADEKA), sumilizer GM, copper GS, copper MDP-S, copper BBM-S copper WX-R copper GA- (Manufactured by BASF), Yoshinox BHT, and Yoshinox BHT were used in the same manner as in Example 1. The results are shown in Table 1. &lt; tb &gt; &lt; TABLE &gt; Dongbu Corp., Dongbu 2246G, Dongbu 425, Dongbu 250, Dongbu 930, Dongbu SS, Dong TT, Dongbu 917 and Dongbu 314 (manufactured by API Corporation).

Of these, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl- 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and 2,6-di-t-butyl-4-cresol are more preferable.

The content of [D] antioxidant is preferably 0.001 part by mass or more and 5 parts by mass or less, more preferably 0.01 parts by mass or more and 2 parts by mass or less, based on 100 parts by mass of the [A1] polymer. By setting the content of [D] antioxidant within the above range, it is possible to effectively prevent oxidation deterioration over time of the cured film obtained.

<[E] Surfactant>

[E] Surfactant is a component that improves film formability. Examples of the [E] surfactant include a fluorine surfactant, a silicone surfactant, and other surfactants.

As the fluorine-based surfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least one of a terminal, a main chain and a side chain is preferable, and for example, a 1,1,2,2-tetrafluoro- (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, hexaethylene glycol di (1,2,2,3,3-hexafluoro-n-pentyl) ether, octaethylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di Hexafluoro-n-pentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, perfluoro- Sodium dodecanesulfonate, 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 Perfluoroalkylpolyoxyethylene, perfluoroalkylpolyoxyethylene, perfluoroalkylpolyoxyethylene, perfluoroalkylpolyoxyethylene, perfluoroalkylalkoxylate, carboxylic acid fluoro, and the like. Alkyl esters and the like.

Examples of commercially available products of the above fluorinated surfactants include BM-1000, BM-1100 (manufactured by BM CHEMIE), Megaface F142D, Copper F172, Copper F173, Copper F183, Copper F178, Copper F191, Copper F471 and F476 (all manufactured by Dainippon Ink and Chemicals, Incorporated), Fluorad FC-170C, Copper-171, Copper-430, Copper-431 (manufactured by Sumitomo 3M Limited), Surplon S- SC-101, SC-102, SC-103, SC-104, SC-105, SC-101 (manufactured by Asahi Glass Co., Ltd.) (Manufactured by Shin-Akita Kasei Co., Ltd.), Fotogent FT-100, -110, -140A, -150, -250, -251, -300, and -352 -310, -400S, FTX-218, and -251 (manufactured by NEOS).

Examples of commercially available products of the silicone surfactants include TORAY Silicon DC3PA, Copper DC7PA, Copper SH11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA, Copper SH-190, Copper SH-193, Copper SZ- TSF-4440, TSF-4440, TSF-4445, TSF-4446, TSF-4460 and TSF-4452 GE Toshiba Silicones), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

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

Examples of commercially available products of the above other surfactants include (meth) acrylic acid type copolymer Polyflow No. 57 and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

The content of the [E] surfactant is preferably 0.01 parts by mass or more and 3 parts by mass or less, more preferably 0.05 parts by mass or more and 1 part by mass or less, based on 100 parts by mass of the polymer [A1]. When the content of the [E] surfactant is within the above range, the film formability can be effectively improved.

<[F] Adhesion aid>

[F] Adhesion-assisting agent is a component that improves the adhesion between the resulting cured film and the substrate. [F] As the adhesion assisting agent, a functional silane coupling agent having a reactive functional group such as a carboxyl 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,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

[F] The content of the adhesion promoter is preferably 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.1 parts by mass or more and 15 parts by mass or less, based on 100 parts by mass of the polymer [A1].

&Lt; Process for producing cured film-forming resin composition (1)

The resin composition (1) for forming a cured film of the present invention can be prepared by mixing the [A1] polymer and, if necessary, other components at a predetermined ratio, preferably in a suitable solvent. The resin composition (1) for forming a cured film, which is produced, is preferably filtered, for example, with a filter having a pore size of about 0.2 탆.

As the solvent used in the production of the resin composition for forming a cured film (1), it is necessary to uniformly dissolve or disperse each component contained in the resin composition (1) for curing film formation, do. Examples of the solvent include an alcohol solvent, an ether solvent, a ketone solvent, an amide solvent, an ester solvent, a hydrocarbon solvent and the like.

As the alcohol-based solvent, for example,

As the monoalcohol-based solvent, it is preferable to use at least one solvent selected from the group consisting of methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, Heptanol, sec-heptanol, 3-heptanol, n-octanol, sec-hexanol, sec-hexanol, sec- Sec-octadecyl alcohol, sec-tetradecyl alcohol, sec-tetradecyl alcohol, sec-octadecanol, sec-octadecyl alcohol, Heptadecyl alcohol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol and the like;

Examples of polyhydric alcohol solvents include polyhydric alcohols such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl- , 4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and the like;

Examples of the polyhydric alcohol partial ether solvent include 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- Diethyleneglycol monoethyl ether, diethyleneglycol monopropyl ether, diethyleneglycol monobutyl ether, diethyleneglycol monohexyl ether, propyleneglycol monomethyl ether, propyleneglycol monoethyl ether, diethyleneglycol monomethylether, diethyleneglycol monomethylether, , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether.

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, -Butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, Acetonyl acetone, acetophenone, and the like.

Examples of the amide solvent include N, N'-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, N, Amide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone and the like.

Examples of the ester solvents include methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec- 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate , Methyl acetoacetate, ethyl acetoacetate, acetic acid ethylene glycol monomethyl ether, acetic acid ethylene glycol monoethyl ether, acetic acid ethylene glycol mono-n-propyl ether, acetic acid ethylene glycol mono-n-butyl ether, acetic acid diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl ether acetate, di Propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoacetate acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, Ethyl lactate, ethyl lactate, ethyl lactate, n-butyl lactate, n-butyl lactate, n-butyl methacrylate, - amyl, diethyl malonate, dimethyl phthalate, diethyl phthalate and the like.

As the hydrocarbon-based solvent, for example,

Examples of the aliphatic hydrocarbon solvent include aliphatic hydrocarbons such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, Methylcyclohexane and the like;

Examples of the aromatic hydrocarbon solvents include aliphatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-propylbenzene, n-amylnaphthalene, and the like.

In addition, the solvent may further contain a high boiling solvent such as caproic acid, caprylic acid, ethylene carbonate, propylene carbonate and the like.

&Lt; Method of forming a 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 the substrate (hereinafter also referred to as "step (A1)") using the resin composition for forming a cured film (1)

(2) a step of heating the coating film (hereinafter also referred to as "step (A2)"),

Respectively.

Since the cured film-forming resin composition (1) has the above properties, according to the method (1) for forming a cured film of the present invention, satisfactory general characteristics such as heat resistance, chemical resistance, transmittance, A cured film having a surface hardness can be formed. Each step will be described in detail below.

[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, preferably by prebaking to remove the solvent to 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 containing plastics such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethersulfone, polycarbonate, and polyimide.

As a coating method, a suitable method such as a spraying method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an ink jet method and the like can be adopted. Among these, spin coating method, bar coating method and slit die coating method are preferable. The conditions for the prebaking may vary depending on the kind of each component, the use ratio, and the like, and may be, for example, 60 to 130 DEG C for 30 seconds to 10 minutes. The film thickness of the formed coating film is preferably 0.1 占 퐉 to 8 占 퐉, more preferably 0.1 占 퐉 to 6 占 퐉, and still more preferably 0.1 占 퐉 to 4 占 퐉, as a value after pre-baking.

[Step (A2)]

In this step, the coating film is cured by heating. The heating method is not particularly limited, but heating can be performed by using a heating device such as an oven or a hot plate. The heating temperature in this step is preferably 200 DEG C or less. Since the curable film can be heated at such a low temperature, the method (1) for forming a cured film can be preferably used for forming a cured film such as an interlayer insulating film on a plastic substrate of a flexible display. The heating temperature is more preferably 120 ° C to 180 ° C, and further preferably 120 ° C to 150 ° C. The heating time varies depending on the type of the heating apparatus. For example, the heating time may be 5 minutes to 40 minutes in the case of performing heat treatment on a hot plate, 30 minutes to 80 minutes in the case of performing heat treatment in an oven, Is within 30 minutes in the case of performing the heat treatment on the hot plate and within 60 minutes in the case of performing the heat treatment in the oven. In this way, a desired cured film 1 such as an interlayer insulating film can be formed on the substrate.

&Lt; Cured film (1) >

The cured film (1) of the present invention is formed from the cured film-forming resin composition (1). The method of forming the cured film 1 is not particularly limited, but it can be preferably formed using the method (1) for forming a cured film described above. Since the cured film 1 is formed from the resin composition 1 for forming a cured film, it can have satisfactory surface hardness and satisfactory general characteristics such as chemical resistance, heat resistance, transmittance and relative dielectric constant. Since the cured film 1 has the above characteristics, it is preferable as an interlayer insulating film, a spacer, a protective film, and a coloring pattern for a color filter of a display element, for example.

&Lt; Negative-type radiation-sensitive resin composition (2) >

The negative radiation-sensitive resin composition (2) of the present invention contains the [A2] polymer, the [B] polymerizable compound and the [C] radiation-sensitive polymerization initiator. The negative-tone radiation-sensitive resin composition (2) may also contain [D] an antioxidant as a suitable component. The negative radiation-sensitive resin composition (2) may contain other optional components other than the components [A] to [D] within the range not impairing the effects of the present invention.

Since the negative radiation-sensitive resin composition (2) contains the [A2] polymer, the [B] polymerizable compound and the [C] radiation-sensitive polymerization initiator, the portion irradiated with the radiation Called negative radiation-sensitive resin composition having so-called negative type radiation-curable resin composition which is cured by an alkali developer to dissolve and remove a portion (unexposed portion) other than the exposed portion to form a pattern. Therefore, the negative-tone radiation-sensitive resin composition (2) can form a patterned cured film. Each component will be described in detail below.

<[A2] Polymer>

[A2] The polymer is a polymer having the structural unit (I) and the structural unit (II-2). Further, the [A2] polymer may have the structural unit (III) and the structural unit (IV) within the range not to impair the effect of the present invention. (A2) Since the polymer has the structural unit (I) and the structural unit (II-2), the negative radiation-sensitive resin composition (2) It is possible to form a cured film sufficiently satisfying general characteristics such as hardness, sensitivity, developing adhesion, chemical resistance, heat resistance, transmittance and relative dielectric constant, and is excellent in storage stability. In addition, the negative-tone radiation-sensitive resin composition (2) can be obtained by subjecting the negative-tone radiation-sensitive resin composition (2) to a method of easily separating hydrogen atoms from alcoholic hydroxyl groups due to electron withdrawing properties of fluorinated alkyl groups of the groups represented by the formula (1) It shows acidity due to the ease of leaving hydrogen atoms of the phenolic hydroxyl groups due to the electron attracting property of the halogen atom and / or the fluorinated alkyl group, and as a result, the development residue due to the alkali developing solution in the unexposed area can be reduced. Further, the [A2] polymer may have two or more kinds of structural units.

[Structural unit (I)]

The structural unit (I) is a structural unit comprising at least one kind selected from the group consisting of the group represented by the above-mentioned formula (1) and the group represented by the above-mentioned formula (2).

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

The content of the structural unit (I) is preferably from 5 mol% to 90 mol%, more preferably from 20 mol% to 80 mol%, and still more preferably from 30 mol% to 80 mol% based on the total structural units constituting the polymer [A2] Or more and 70 mol% or less. When the content ratio of the structural unit (I) is within the above range, storage stability and the like can be effectively improved.

[Structural unit (II-2)]

The structural unit (II-2) is a structural unit containing a crosslinkable group (a2).

Examples of the structural unit (II-2) include structural units similar to those exemplified above for structural unit (II-1).

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

The content of the structural unit (II-2) is preferably from 1 mol% to 70 mol%, more preferably from 5 mol% to 50 mol%, and still more preferably from 10 mol% to 10 mol%, based on the total structural units constituting the polymer [A2] Mol% or more and 30 mol% or less. When the content ratio of the structural unit (II-2) is within the above range, storage stability and the like can be effectively improved.

[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) acrylate ester having a hydroxyl group or a compound represented by the following formula (3). [A2] When the polymer has the structural unit (III), it is possible to control the alkali developing property and to suppress the residue.

In the above formula (3), R 'is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with a fluorine atom. Each of R ^L1 to R ^L5 independently represents 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 to 3; Provided that 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 above.

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

In the 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). As the structural unit (III), structural units represented by the formulas (III-1), (III-4) and (III-10) are preferable.

Examples of the monomer compound that provides the structural unit (III) include 2-hydroxyethyl methacrylate, 4-hydroxyphenyl methacrylate, o-hydroxystyrene, p- hydroxystyrene, Styrene is preferable, and 2-hydroxyethyl methacrylate, 4-hydroxyphenyl methacrylate and? -Methyl-p-hydroxystyrene are more preferable.

The content of the structural unit (III) is preferably from 0 mol% to 50 mol%, more preferably from 1 mol% to 30 mol%, still more preferably from 3 mol% to 30 mol% based on the total structural units constituting the polymer [A2] Or more and 20 mol% or less.

[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). The polymer [A2] has the structural unit (IV), whereby the negative radiation-sensitive resin composition (2) can be prepared by adjusting the glass transition temperature of the resin to improve the alkali developing property, the melt flowability upon thermal curing, Strength and chemical resistance can be improved.

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

In the 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 to 10; As the structural unit (IV), structural units represented by the formulas (IV-1), (IV-2), (IV-7) to (IV-9) and (IV-11) are preferable.

Examples of the monomer compound that provides the structural unit (IV) include monomers such as (meth) acrylic acid, (meth) acrylic acid chain alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid diester, Unsaturated aromatic compounds and conjugated diene compounds, and unsaturated compounds having a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyrazene skeleton, or a skeleton represented by the following formula (4) And a structural unit derived from an unsaturated compound or the like.

In the above formula (4), R ^M and s are as defined in the above formulas (IV-1) to (IV-11).

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

Examples of the (meth) acrylic acid cyclic alkyl esters include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, tricyclo [5.2.1.0 ^{2 6} ] decane-8-yloxyethyl, acrylic acid cyclic alkyl esters such as isobornyl acrylate; 2-methylcyclohexyl methacrylate, tricyclohexyl methacrylate [5.2.1.0 ^2,6 ] decane-8-yl, methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8 Methacrylic acid cyclic alkyl esters such as monoethyl, monoethyl, monoethyl, monoethyl, monoethoxy and monoethoxy.

Examples of the (meth) acrylic acid aryl esters include acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; Methacrylic acid aryl esters 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 above-mentioned non-cyclic unsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [ 2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] hept- 2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (t-butoxycarbonyl) bicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2 (Hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dihydroxycyclo [2.2.1] hept- Ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept- -Hydroxy-5-ethyl Bicyclo [2.2.1] hept-2-ene, and the like can be mentioned 5-hydroxy-5-methyl [2.2.1] hept-2-ene.

Examples of the maleimide compound include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) Maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide Propionate, N- (9-acridinyl) maleimide, and the like.

Examples of the unsaturated aromatic compound include styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene and? -Methyl-p-hydroxystyrene.

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-methacryloyloxypropionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one, (meth) acrylic acid Tetrahydrofurfuryl, tetrahydro (meth) acrylate, and the like.

Examples of the unsaturated compound having a furan skeleton include 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, Methyl-1-hexen-3-one, 6-furan-2-one, Methyl-ethyl ester, 6- (2-furyl) -6-methyl-1-ene- And the like.

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

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

Examples of the unsaturated compound having a skeleton represented by the formula (4) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (Meth) 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 them, as the monomer compound providing the structural unit (IV), there may be mentioned a methacrylic acid chain alkyl ester, a methacrylic acid cyclic alkyl ester, a maleimide compound, a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, Unsaturated compounds, unsaturated aromatic compounds and acrylic acid cyclic alkyl esters having a skeleton represented by the above general formula (4) are preferable, and styrene, methacrylic acid, methyl methacrylate, methacrylic acid and methacrylic acid are preferable in terms of copolymerization reactivity and solubility in an aqueous alkali solution. Butyl acrylate, n-lauryl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, (Meth) acrylic acid tetrahydrofurfuryl, polyethylene glycol (n = 2 to 10) mono (meth) acrylate, 3- (meth) acryloyloxytetrahydro It is more preferably 2-one.

The content of the structural unit (IV) is preferably from 0 mol% to 90 mol%, more preferably from 1 mol% to 70 mol%, still more preferably from 3 mol% to 70 mol%, based on the total structural units constituting the polymer [A2] Or more and 60 mol% or less. By setting the content ratio of the structural unit (IV) within the above range, the chemical resistance can be effectively improved.

<Method of synthesizing [A2] polymer>

[A2] The method for synthesizing the polymer is not particularly limited, and for example, the same method as the synthesis method of the above-mentioned [A1] polymer can be applied.

The weight average molecular weight (Mw) of the polymer [A2] in terms of polystyrene determined by gel permeation chromatography (GPC) is preferably 1,000 or more and 30,000 or less, and more preferably 5,000 or more and 20,000 or less. By setting the Mw of the polymer [A2] within the above range, the sensitivity and developability of the negative radiation-sensitive resin composition (2) can be further improved. The ratio (Mw / Mn) of the Mw of the polymer [A2] to the polystyrene reduced number average molecular weight (Mn) by GPC is preferably 1 or more and 3 or less, more preferably 1.5 or more and 2.5 or less.

&Lt; [B] Polymerizable compound >

[B] The polymerizable compound is a compound having an ethylenic unsaturated bond. The [B] polymerizable compound may be used alone or in combination of two or more.

The polymerizable compound [B] is not particularly limited as long as it is a polymerizable compound having an ethylenically unsaturated bond, and examples thereof include ω-carboxypolycaprolactone mono (meth) acrylate, 2- (2'-vinyloxyethoxy) ethyl (Meth) acrylate; a monofunctional (meth) acrylate compound such as (meth) acrylate; (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (Meth) acrylate, dimethanol tricyclodecane di (meth) acrylate, dipropylene glycol di (meth) acrylate, bisphenoxyethanol fluorene di Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) (Meth) acryloyloxyethyl) phosphate, ethylene oxide-modified dipentaerythritol hexaacrylate, succinic acid-modified pentaerythritol triacrylate (Meth) acryloyloxy group having at least one hydroxyl group in the molecule and a compound having at least two isocyanate groups and having at least one hydroxyl group in the molecule and a compound having three or more (Meth) acrylate compounds, and the like.

As a commercially available product of the polymerizable compound [B], for example,

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-9050, Aronix TO-1450 and TO-1382 (all manufactured by Toa Kosei);

KAYARAD DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120 and MAX-3510 (manufactured by Nippon Kayaku Co., Ltd.);

Viscoat 295, Copper 300, Copper 360, Copper GPT, Copper 3PA, Copper 400 (manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.);

As the urethane acrylate compound, New Frontier R-1150 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.);

KAYARAD DPHA-40H, UX-5000 (manufactured by Nippon Kayaku Co., Ltd.);

UN-9000H (manufactured by Negami Chemical Industry Co., Ltd.);

270, M-6200, M-305, M-309, M-309, M- Dong M-310, Dong M-315 (manufactured by Toagosei Co., Ltd.);

KAYARAD HDDA, KAYARAD HX-220, HX-620, R-526, R-167, R-604, R-684, R-551, R-712, UX-2201 and UX-2301 , UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937, MU-2100, MU-4001 (manufactured by Nippon Kayaku Co., Ltd.);

Art Resin UN-9000PEP, UN-9200A, UN-7600, UN-333, UN-1003, UN-1255, UN-6060P, UN-6060P (manufactured by Negami Kogyo Co., Ltd.);

SH-500B Viscoat 260, Copper 312, Copper 335HP (manufactured by Osaka Yuki Kagaku Kogyo) and the like.

The [B] polymerizable compound preferably has at least one carboxyl group in the same molecule. As a result, it is possible to improve the crosslinking property and reduce the development residue in the unexposed area. As the [B] polymerizable compound having at least one carboxyl group in the same molecule, ω-carboxypolycaprolactone mono (meth) acrylate and succinic acid-modified pentaerythritol triacrylate are preferable.

The content of the [B] polymerizable compound is preferably 20 parts by mass or more and 200 parts by mass or less, more preferably 40 parts by mass or more and 160 parts by mass or less, based on 100 parts by mass of the polymer [A2]. By setting the content of the polymerizable compound [B] within the above range, the negative radiation-sensitive resin composition (2) can form a cured film having excellent adhesiveness and sufficient surface hardness even at a low exposure dose.

<[C] Radiation-induced Polymerization Initiator>

[C] The radiation-sensitive radiation polymerization initiator is a component which generates an active species capable of initiating polymerization of the [B] polymerizable compound in response to radiation. Examples of the [C] radiation-sensitive polymerization initiator include oxime ester compounds, acetophenone compounds, and imidazole compounds. The [C] radiation-sensitive polymerization initiator may be used alone or in combination of two or more.

Examples of the oxime ester compound include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- -9-ethyl-6-benzoyl-9H-carbazol-3-yl] -octan-1-one Oxal-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- Yl) -ethan-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl Yl) -1- (O-acetyloxime), ethanone- 1- [9-ethyl-6- (2-methyl-4-tetrahydrobenzoyl) -9H- Ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) - 9H-carbazol-3-yl] -1- (O- acetyloxime) 3-yl] -1- (O-acetyloxime), ethanone- 1- [9-ethyl-6- {2-methyl- Solanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O- Butyl-oxime), and the like O- acyl oxime compounds such as. Of these, oxime ester compounds include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- (9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H -Carbazol-3-yl] -1- (O-acetyloxime), ethanone- 1- [9-ethyl- 6- {2-methyl- 4- (2,2- Yl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) is preferred.

Examples of the acetophenone compound include an? -Amino ketone compound and? -Hydroxyketone compound.

Examples of the? -Amino ketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- -1- (4-morpholin-4-yl-phenyl) -butan-1-one and 2-methyl-1- (4-methylthiophenyl) have.

Examples of the? -Hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) 1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone and 1-hydroxycyclohexyl phenyl ketone.

As the acetophenone compound, an? -Amino ketone compound is preferable, and 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one is more preferred.

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) Bisimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- Dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) , 5'-tetraphenyl-1,2'-biimidazole, and the like. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2', 5'-tetraphenyl- - nonimidazole is more preferred.

Examples of commercially available products of the [C] radiation-sensitive polymerization initiator include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (Irgacure 907) (Irgacure 379), 1,2-octanedione-l- [4- ((4-methylphenyl) (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1 - (O-acetyloxime) (Irgacure OXE02) (manufactured by Ciba Specialty Chemicals), and the like.

The content of the [C] radiation-sensitive polymerization initiator is preferably 0.1 parts by mass or more and 40 parts by mass or less, more preferably 0.5 parts by mass or more and 20 parts by mass or less, based on 100 parts by mass of the polymer [A2]. By setting the content of the [C] radiation-sensitive polymerization initiator within the above range, the negative radiation-sensitive resin composition (2) can form a cured film having sufficient surface hardness and adhesion even at a low exposure dose.

The content of the oxime ester compound is preferably 0.1 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the polymer [A2], more preferably 1 part by mass or more and 5 mass parts by mass Or less. This makes it possible to efficiently form a cured film having sufficient surface hardness and adhesion even in the case of a low exposure dose.

<[D] Antioxidant>

[D] The antioxidant is a component capable of decomposing a radical generated by exposure or heating, or a peroxide generated by oxidation, and preventing the decomposition of bonding of polymer molecules. As the [D] antioxidant, the antioxidant described in the section of the above-mentioned &quot; resin composition for forming a cured film (1) &quot; The negative-tone radiation-sensitive resin composition (2) contains the [D] antioxidant to prevent the deterioration of the cured film with time over time, and can suppress the change in the thickness of the cured film, for example. The antioxidant [D] may be used alone or in combination of two or more.

The content of [D] antioxidant is preferably 0 parts by mass or more and 5 parts by mass or less, more preferably 0.01 parts by mass or more and 2 parts by mass or less, based on 100 parts by mass of the polymer [A2]. By setting the content of [D] antioxidant within the above range, it is possible to effectively prevent oxidation deterioration over time of the cured film obtained.

<Other optional components>

Examples of other optional components that the negative-tone radiation-sensitive resin composition (2) may contain include [E] a surfactant, [F] an adhesion aid and the like in addition to a solvent. For each of the other optional components, those described in the section of the above-mentioned &quot; Resin composition for forming a cured film (1) &quot;

&Lt; Method for producing negative-tone radiation-sensitive resin composition (2)

The negative-tone radiation-sensitive resin composition (2) of the present invention can be prepared by mixing the [A2] polymer and, if necessary, other components in a predetermined ratio, preferably in a suitable solvent. Examples of the solvent used in the production of the negative-tone radiation-sensitive resin composition (2) include a solvent similar to the solvent exemplified in the above-mentioned &quot; Process for producing a cured film-forming resin composition (1) can do. The negative-tone radiation-sensitive resin composition (2) thus prepared is preferably filtered with a filter having a pore size of about 0.2 m, for example.

&Lt; Method of forming a cured film (2) >

In the method (2) for forming a cured film of the present invention,

(1) a step of forming a coating film on the substrate (hereinafter also referred to as "step (B1)") using the negative radiation sensitive resin composition (2)

(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 also referred to as "step (B4)"),

Respectively.

According to the method (2) for forming a cured film of the present invention, since the negative type radiation sensitive resin composition (2) has the above properties, it is possible to satisfactorily satisfy general characteristics such as heat resistance, chemical resistance, transmittance, A cured film having excellent surface hardness can be formed. Each step will be described in detail below.

[Step (B1)]

In this step, a coating film is formed on the substrate by using the negative radiation-sensitive resin composition (2). Specifically, the solution of the negative-tone radiation-sensitive resin composition (2) is coated on the surface of the substrate, preferably by prebaking to remove the solvent to 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 containing plastics such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethersulfone, polycarbonate, and polyimide.

As a coating method, a suitable method such as a spraying method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an ink jet method and the like can be adopted. Among these, spin coating method, bar coating method and slit die coating method are preferable. The conditions for the prebaking may vary depending on the kind of each component, the use ratio, and the like, and may be, for example, 60 to 130 DEG C for 30 seconds to 10 minutes. The film thickness of the formed coating film is preferably 0.1 占 퐉 to 8 占 퐉, more preferably 0.1 占 퐉 to 6 占 퐉, and still more preferably 0.1 占 퐉 to 4 占 퐉, as a value after pre-baking.

[Step (B2)]

In this step, a part of the coating film is irradiated with radiation. Specifically, the coated film formed in the step (B1) is irradiated with a radiation through a mask having a predetermined pattern. Examples of the radiation used at this time include ultraviolet rays, deep ultraviolet rays, X-rays, charged particle rays, and the like.

Examples of the ultraviolet ray include g-line (wavelength: 436 nm) and i-line (wavelength: 365 nm). Examples of the far ultraviolet ray include KrF excimer laser light and the like. Examples of X-rays include synchrotron radiation. Examples of the charged particle beam include electron beams and the like. Of these radiation, ultraviolet rays are preferable, and among ultraviolet rays, radiation including g line, h line and / or i line is more preferable. Examples of radiation exposure dose, 0.1J / m ² to 10,000J / m ² is preferred.

[Step (B3)]

In this step, the coated film irradiated with the radiation is developed. Specifically, the coating film irradiated with the radiation in the step (B2) is developed with a developer to remove the irradiated portion of the radiation. Examples of the developer include aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, Amine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0 ] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonane, and the like. Further, an aqueous solution containing an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, or a surfactant, or an aqueous alkali solution containing a small amount of various organic solvents capable of dissolving the negative-tone radiation-sensitive resin composition (2) .

As the developing method, a suitable method such as a liquid-solid method, a dipping method, a swing dipping method, a shower method and the like can be adopted. The development time varies depending on the composition of the negative radiation-sensitive resin composition (2), but may be, for example, 30 seconds to 120 seconds. Further, after the development process, the patterned coating film is subjected to a rinsing treatment by running water washing, and then irradiated (post-exposure) with radiation by a high-pressure mercury lamp or the like on the entire surface to remove the [C] radiation- It is preferable to carry out the decomposition treatment of the polymerization initiator. The exposure amount in the subsequent 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 heat treatment (post-baking) using a heating device such as a hot plate or oven for heating the developed coating film in step B3. The heating temperature in this step is preferably 200 DEG C or less. In addition to the ability to form fine patterns using the radiation-sensitive properties, the method (2) 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 . The heating temperature is more preferably 120 ° C to 180 ° C, and further preferably 120 ° C to 150 ° C. The heating time varies depending on the type of the heating apparatus. For example, the heating time may be 5 minutes to 40 minutes in the case of performing heat treatment on a hot plate, 30 minutes to 80 minutes in the case of performing heat treatment in an oven, Is within 30 minutes in the case of performing the heat treatment on the hot plate and within 60 minutes in the case of performing the heat treatment in the oven. In this way, a pattern-like coating film corresponding to a target cured film such as an interlayer insulating film can be formed on the substrate.

&Lt; Cured film (2) >

The cured film (2) of the present invention is formed from the negative radiation-sensitive resin composition (2). The method of forming the cured film 2 is not particularly limited, but it can be preferably formed using the method (2) for forming a cured film described above. Since the cured film 2 is formed from the negative radiation-sensitive resin composition 2, it can have satisfactory surface hardness and satisfactory general characteristics such as chemical resistance, heat resistance, transmittance and relative dielectric constant . The cured film 2 is preferable as an interlayer insulating film of a display element, a spacer, a protective film, a coloring pattern for a color filter, and the like because it has the above characteristics.

<Semiconductor device>

The semiconductor device of the present invention includes the cured film (the cured film (1) or the cured film (2) described above). This cured film is used, for example, as an interlayer insulating film or the like for insulating between wirings in the semiconductor element. The semiconductor device can be formed using a known method. Since the semiconductor device includes the cured film, it can be suitably used for electronic devices such as display devices, LEDs, and solar cells.

<Display element>

The display element of the present invention comprises the above semiconductor element. Since the display element includes the semiconductor element having the cured film, general characteristics required for practical use as a display element are satisfied. Examples of the display element include a liquid crystal display element and the like. In the liquid crystal display element, for example, two TFT array substrates each having a liquid crystal alignment film formed on its surface are arranged opposite to each other on the liquid crystal alignment film side through a sealant provided in the peripheral portion of the TFT array substrate. The liquid crystal is filled. The TFT array substrate has wires arranged in layers, and the wires are insulated by the cured film as an interlayer insulating film.

&Lt; Positive-type radiation-sensitive resin composition >

The positive radiation-sensitive resin composition of the present invention contains the [A3] polymer and the [G] acid generator. In addition, the positive radiation-sensitive resin composition may contain a [H] solvent as a suitable component. The positive radiation-sensitive resin composition may contain other optional components as long as the effect of the present invention is not impaired. Each component will be described in detail below.

<[A3] Polymer>

[A3] The polymer is a polymer having the structural units (I) and (II-3). Further, the [A3] polymer may have the structural unit (III) and the structural unit (IV) within the range not to impair the effect of the present invention. Further, the [A3] polymer may have two or more kinds of structural units.

[Structural unit (I)]

The structural unit (I) is a structural unit comprising at least one kind selected from the group consisting of the group represented by the above-mentioned formula (1) and the group represented by the above-mentioned formula (2). By having the structural unit (I) and the structural unit (II-3) described later, the positive-tone radiation-sensitive resin composition is excellent in storage stability while maintaining good surface hardness, It is possible to form a cured film which can sufficiently satisfy general characteristics such as adhesion, heat resistance, chemical resistance, transmittance and relative dielectric constant. This is because the hydroxyl groups in the groups represented by the formulas (1) and / or (2) contained in the structural unit (I) and the cyclic ether and / or cyclic carbonate contained in the structural unit (II- It is presumed that the surface hardness of the cured film can be maintained by the formation of a strong crosslinked structure and that the reaction does not proceed at room temperature and as a result the thickening is inhibited during storage and good storage stability is obtained.

In the above 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 at least one of R ¹ and R ² is a fluorinated alkyl group having 1 to 4 carbon atoms.

In the 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. Provided that at least one of R ³ and R ⁴ is a halogen atom or a fluorinated alkyl group having 1 to 4 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹ to R ⁴ include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i- -Butyl group and the like.

The fluorinated alkyl group having 1 to 4 carbon atoms represented by R ¹ to R ⁴ is a group in which a part or all of the hydrogen atoms contained in the alkyl group having 1 to 4 carbon atoms is substituted with a fluorine atom. Examples of the alkyl group having 1 to 4 carbon atoms include the same groups as those exemplified as the alkyl group having 1 to 4 carbon atoms represented by R ¹ to R ⁴ .

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

As R ¹ to R ⁴ , a fluorinated alkyl group having 1 to 4 carbon atoms and a halogen atom are preferable. As the fluorinated alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms is more preferable, and a trifluoromethyl group is more preferable. The halogen atom is more preferably a fluorine atom.

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

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

R ⁵ and as the monovalent organic group (n + 1) represented by R ^6, for example having 1 to 20 carbon atoms in the (n + 1) valent chain hydrocarbon group, having 3 to 20 (n + 1) valent alicyclic hydrocarbon (N + 1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms, a linear hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms (N + 1) -valent groups obtained by combining the above-mentioned groups. However, some or all of the hydrogen atoms of these groups may be substituted.

Examples of the (n + 1) th chain hydrocarbon group having 1 to 20 carbon atoms include groups obtained by removing n hydrogen atoms from a linear or branched alkyl group having 1 to 20 carbon atoms.

Examples of the straight-chain or branched alkyl group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, -Butyl group and the like.

Examples of the (n + 1) -valent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a group obtained by removing n hydrogen atoms from a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms.

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 obtained by removing n hydrogen atoms from a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

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

Among them, R ⁵ is preferably a chain hydrocarbon group, an alicyclic hydrocarbon group, and a group combining these groups, and examples thereof include ethylene, 1,2-propylene, 2,5- Group is more preferable. As R ⁶ , a divalent aromatic hydrocarbon group is preferable, and a phenylene group is more preferable.

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

In the above formulas (2a) and (2b), R is as defined in the above formulas (1a) and (1b). R ³ and R ⁴ are as defined 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 the above formulas, R is synonymous with the above formulas (1a), (1b), (2a) and (2b). Among them, the structural unit represented by the formula (I-1) to (I-6), (I-9) and (I-11) to (I- (I-1) to (I-6) are more preferable from the viewpoints of heat resistance, heat resistance and heat and curability.

The content of the structural unit (I) is preferably from 10 to 90 mol%, more preferably from 20 to 80 mol%, and still more preferably from 30 to 30 mol%, based on the total structural units constituting the polymer [A3] Or more and 70 mol% or less. By setting the content ratio of the structural unit (I) within the above range, the storage stability and the like can be effectively improved.

[Structural unit (II-3)]

The structural unit (II-3) is a structural unit containing a cyclic ether structure or a cyclic carbonate structure.

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

As the structural unit (II-3), for example,

Structural units represented by the following formulas (II-1) to (II-5), including oxirane structures;

Structural units represented by the following formulas (II-6) to (II-9), including oxetane structures;

Structural units represented by the following formulas (II-10) and (II-11), including a tetrahydrofuran structure;

Structural units represented by the following formulas (II-12) to (II-16), including cyclic carbonate structures, and the like.

In the formulas (II-1) to (II-16), R ⁷ is a hydrogen atom, a methyl group or a trifluoromethyl group. (II-1) to (II-9) and (II-12) to (II-16) are preferable from the viewpoints of the crosslinking property and the chemical resistance , More preferably a structural unit represented by any one of formulas (II-1) to (II-9), still more preferably a structural unit represented by formulas (II- 1) to (II-3) are particularly preferable.

The content of the structural unit (II-3) is preferably from 1 mol% to 70 mol%, more preferably from 5 mol% to 50 mol%, and still more preferably from 10 mol% to 10 mol%, based on the total structural units constituting the polymer [A3] Mol% or more and 30 mol% or less. By setting the content ratio of the structural unit (II-3) within the above range, the storage stability and the like can be effectively improved.

It is preferable that the structural unit (II-3) includes a cyclic ether structure, and the cyclic ether structure is at least one of an oxirane structure and an oxetane structure. By including the above-mentioned structural unit (II-3), the crosslinking property can be improved, and as a result, the positive radiation-sensitive resin composition can improve the surface hardness, heat resistance and the like.

[Structural unit (III)]

The structural unit (III) is a structural unit derived from a (meth) acrylate ester having a hydroxyl group or a structural unit derived from a compound represented by the following formula (3). [A3] By having the polymer having the structural unit (III), it is possible to control the alkali developing property and to suppress the residue.

In the above formula (3), R 'is a hydrogen atom or an alkyl having 1 to 4 carbon atoms which may be substituted with a fluorine atom. Each of R ^L1 to R ^L5 independently represents 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 to 3; Provided that 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 above.

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

In the 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). As the structural unit (III), structural units represented by the formulas (III-1), (III-4) and (III-10) are preferable.

Examples of the monomer compound that provides the structural unit (III) include 2-hydroxyethyl methacrylate, 4-hydroxyphenyl methacrylate, o-hydroxystyrene, p- hydroxystyrene, Styrene is preferable, and 2-hydroxyethyl methacrylate, 4-hydroxyphenyl methacrylate and? -Methyl-p-hydroxystyrene are more preferable.

The content of the structural unit (III) is preferably from 0 mol% to 50 mol%, more preferably from 1 mol% to 30 mol%, still more preferably from 3 mol% to 30 mol% based on the total structural units constituting the polymer [A3] Or more and 20 mol% or less.

[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). [A3] By having the polymer having the structural unit (IV), the alkali transferability, the melt flowability upon thermal curing, the mechanical strength of the cured film, and the chemical resistance can be improved by adjusting the glass transition temperature of the resin.

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

In the 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 to 10; As the structural unit (IV), structural units represented by the formulas (IV-1), (IV-2), (IV-7) to (IV-9) and (IV-11) are preferable.

Examples of the monomer compound that provides the structural unit (IV) include monomers such as (meth) acrylic acid, (meth) acrylic acid chain alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid diester, Unsaturated aromatic compounds and conjugated diene compounds, and unsaturated compounds having a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyrazene skeleton, or a skeleton represented by the following formula (4) And a structural unit derived from an unsaturated compound or the like.

In the above formula (4), R ^M and s are as defined in the above formulas (IV-1) to (IV-11).

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

Examples of the (meth) acrylic acid cyclic alkyl esters include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, tricyclo [5.2.1.0 ^{2 6} ] decane-8-yloxyethyl, acrylic acid cyclic alkyl esters such as isobornyl acrylate; 2-methylcyclohexyl methacrylate, tricyclohexyl methacrylate [5.2.1.0 ^2,6 ] decane-8-yl, methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8 Methacrylic acid cyclic alkyl esters such as monoethyl, monoethyl, monoethyl, monoethyl, monoethoxy and monoethoxy.

Examples of the (meth) acrylic acid aryl esters include phenyl acrylate. Acrylic acid aryl esters such as benzyl acrylate; Methacrylic acid aryl esters 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 above-mentioned non-cyclic unsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [ 2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] hept- 2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (t-butoxycarbonyl) bicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2 (Hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dihydroxycyclo [2.2.1] hept- Ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept- -Hydroxy-5-ethyl Bicyclo [2.2.1] hept-2-ene, and the like can be mentioned 5-hydroxy-5-methyl [2.2.1] hept-2-ene.

Examples of the maleimide compound include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) Maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide Propionate, N- (9-acridinyl) maleimide, and the like.

Examples of the unsaturated aromatic compound include styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene and? -Methyl-p-hydroxystyrene.

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 tetrahydrofuran (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran- 2-one, and (meth) acrylate tetrahydrofurfuryl.

Examples of the unsaturated compound having a furan skeleton include 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, Methyl-1-hexen-3-one, 6-furan-2-one, Methyl-ethyl ester, 6- (2-furyl) -6-methyl-1-ene- And the like.

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

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

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

Among them, as the monomer compound providing the structural unit (IV), there may be mentioned a methacrylic acid chain alkyl ester, a methacrylic acid cyclic alkyl ester, a maleimide compound, a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, Unsaturated compounds, unsaturated aromatic compounds and acrylic acid cyclic alkyl esters having a skeleton represented by the above general formula (4) are preferable, and styrene, methacrylic acid, methyl methacrylate, methacrylic acid and methacrylic acid are preferable in terms of copolymerization reactivity and solubility in an aqueous alkali solution. Butyl acrylate, n-lauryl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, (Meth) acrylic acid tetrahydrofurfuryl, polyethylene glycol (n = 2 to 10) mono (meth) acrylate, 3- (meth) acryloyloxytetrahydro It is more preferably 2-one.

The content of the structural unit (IV) is preferably from 0 mol% to 90 mol%, more preferably from 1 mol% to 70 mol%, still more preferably from 3 mol% to 70 mol%, based on the total structural units constituting the polymer [A3] Or more and 60 mol% or less. By setting the content ratio of the structural unit (IV) within the above range, the chemical resistance can be effectively improved.

<Method of synthesizing [A3] polymer>

[A3] The polymer can be produced, for example, by polymerizing monomers corresponding to predetermined structural units in a suitable solvent using a radical initiator. For example, a method in which a solution containing a monomer and a radical initiator is added dropwise to a solution containing a reaction solvent or a monomer to effect polymerization, a solution containing a monomer, and a solution containing a radical initiator, A method in which a solution containing a monomer and a solution containing a radical initiator are separately added dropwise into a reaction solvent or a solution containing a monomer to effect polymerization reaction And the like.

The reaction temperature in these methods may be appropriately determined depending on the initiator species. But it is usually 30 to 180 ° C, preferably 40 to 160 ° C, and more preferably 50 to 140 ° C. The dropping time is usually from 30 minutes to 8 hours, preferably from 45 minutes to 6 hours, more preferably from 1 hour to 5 hours, although it depends on the conditions such as the reaction temperature, the kind of the initiator and the monomer to be reacted. The total reaction time including the dropping time also varies depending on the conditions like the dropping time, but is usually from 30 minutes to 8 hours, preferably from 45 minutes to 7 hours, more preferably from 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) and 2,2'-azobis (2-methylpropionitrile). 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 the polymerization inhibiting solvent (nitrobenzene having polymerization inhibiting effect, mercapto compound having chain transfer effect, etc.), and a solvent in which the monomer is soluble. Examples of the polymerization solvent include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester · lactone solvents and nitrile solvents. These solvents may be used alone or in combination of two or more.

The polymer obtained by the polymerization reaction is preferably recovered by the reprecipitation method. That is, after completion of the polymerization reaction, the polymer solution is put into a re-precipitation solvent to recover the objective polymer as a powder. As the re-precipitation solvent, alcohols, alkanes, etc. may be used alone or in combination of two or more. In addition to the reprecipitation method, a polymer may 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.

[A3] In the polymerization reaction for producing a polymer, a molecular weight adjuster may be used to adjust the molecular weight. Examples of the molecular weight regulator include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexylmercaptan, n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan and thioglycolic acid; Xanthogens such as dimethylxanthogen sulfide and diisopropylxanthogen disulfide; Terpinolene,? -Methylstyrene dimer, and the like.

The weight average molecular weight (Mw) of the polymer [A3] in terms of polystyrene as determined by gel permeation chromatography (GPC) 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. By setting the Mw of the polymer [A3] within the above range, the sensitivity and developability of the positive radiation-sensitive resin composition can be enhanced.

[A3] The ratio (Mw / Mn) of the polymer Mw to the polystyrene reduced number average molecular weight (Mn) by GPC is preferably 1 or more and 3 or less, more preferably 1.5 or more and 2.5 or less.

<[G] acid generator>

[G] The acid generator emits acid by irradiation with radiation or heating. When the positive radiation-sensitive resin composition contains the [G] acid generator, the positive radiation-sensitive characteristic in which the exposed portion of the radiation is removed in the developing step, and the acid generated by heating in the subsequent heating step And functions as a crosslinking catalyst, thereby promoting the crosslinking reaction, thereby forming a cured film having high heat resistance and surface hardness. As the form of containing the [G] acid generator in the positive-tone radiation-sensitive resin composition, a form of the compound (to be referred to as the "[G] acid generator" hereinafter) It may be an inserted aspect as a part, or both of them. The radiation includes a visible ray, an ultraviolet ray, a far ultraviolet ray, an X ray, a charged particle ray, and the like.

Examples of the [G] acid generator include an oxime sulfonate compound, a sulfonimide compound, and a quinone diazide compound. These [G] acid generators may be used alone or in combination of two or more.

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

In the above formula (5), R ^a is an alkyl group having 1 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Provided that some or all of the hydrogen atoms contained in these alkyl groups, alicyclic groups and aryl groups may be substituted by substituents.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ^a include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, And the like. Of these, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable.

Examples of the cycloaliphatic group having 3 to 20 carbon atoms represented by R ^a include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

Examples of the substituent which the alkyl group and the alicyclic group may have include an alkoxy group having 1 to 10 carbon atoms and an alicyclic group having 1 to 10 carbon atoms.

Examples of the alkoxy group having 1 to 10 carbon atoms as the substituent include a methoxy group and an ethoxy group.

As the aliphatic group having 1 to 10 carbon atoms as the substituent, for example, those having 1 to 10 carbon atoms among the alicyclic groups having 3 to 20 carbon atoms represented by R ^a can be applied.

Examples of the aryl group having 6 to 20 carbon atoms represented by R ^a include a phenyl group, a tolyl group, a xylyl group, a naphthyl group and an anthryl group. Of these, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group and a naphthyl group are more preferable.

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

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

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

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

As the compound containing an oxime sulfonate group represented by the above formula (5), oxime sulfonate compounds represented by the following formulas (5-1) and (5-2) are preferable.

In the formulas (5-1) and (5-2), R ^a is the same as in the above formula (5). X is an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, or a halogen atom. and m is an integer of 0 to 3. When m is 2 or 3, plural Xs may be the same or different.

Examples of the alkyl group having 1 to 5 carbon atoms, the alkoxy group having 1 to 5 carbon atoms, and the halogen atom represented by X include the same groups as the groups exemplified as the substituents. Of these, the alkyl group is preferably a straight-chain or branched alkyl group having 1 to 4 carbon atoms, and the alkoxy group is preferably a straight-chain or branched alkoxy group having 1 to 4 carbon atoms. As the halogen atom, The atom is preferred. Also, m is preferably 0 or 1. Particularly, in the above formula (5-1), a compound wherein m is 1, X is a methyl group, and the substitution position of X is an ortho position is preferable.

(5-1-i) to (5-1-iv), and (5-2-i) and (5-2-i) shown below are examples of the oxime sulfonate compound represented by the above- ii), and the like.

Examples of the sulfonimide compounds include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide , N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) naphthyldicarboxyimide (trifluoromethanesulfonic acid-1,8-naphthalimide ), N (phenylsulfonyloxy) naphthyldicarboxylic imide, N (4-methylphenylsulfonyloxy) naphthyldicarboxylic acidimide, N- - (2-trifluoromethylphenylsulfonyloxy) naphthyldicarboxylide, N- (4-fluorophenylsulfonyloxy) naphthyldicarboxylide, N- (pentafluoroethylsulfonyloxy) (Heptafluoropropylsulfonyloxy) naphthyldicarboxylide, N- (nonafluorobutylsulfonyloxy) naphthyldicarboxyimide, N- (Ethylsulfonyloxy) naphthyldicarboxylide, N- (propylsulfonyloxy) naphthyldicarboxyimide, N- (butylsulfonyloxy) naphthyldicarboxyimide, N- (pentylsulfonyloxy) (Heptylsulfonyloxy) naphthyldicarboxyimide, N- (octylsulfonyloxy) naphthyldicarboxyimide, N- (heptylsulfonyloxy) naphthyldicarboxyimide, N- Naphthyldicarboxylic acid imide, and the like, and N- (nonylsulfonyloxy) naphthyldicarboxylimide.

As the quinone diazide compound, for example, a phenolic compound or an alcoholic compound (hereinafter also referred to as a "mother nucleus"), a 1,2-naphthoquinone diazide sulfonic acid halide or a 1,2-naphthoquinone diazide sulfonic acid amide Can be used.

Examples of the above-mentioned mother cores include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother cells other than the above- have.

As specific examples of the above-mentioned mother cells, for example,

As the trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone and the like;

Examples of the tetrahydroxybenzophenone include 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxy Benzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone and the like;

As the pentahydroxybenzophenone, 2,3,4,2 ', 6'-pentahydroxybenzophenone and the like;

As the hexahydroxybenzophenone, 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone and the like;

(Dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tris (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris 4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] -1,3-dihydroxyphenyl) (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'-spirobindene- 7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavone and the like;

(2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 1- [1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl] -3- -Methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl) benzene, 4,6-bis {1- (4- hydroxyphenyl) Hydroxybenzene and the like.

Among them, 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tris (p-hydroxyphenyl) ethane, 4,4 '- [ [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol is preferable.

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

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

In the condensation reaction of the phenolic compound or the alcoholic compound (mother cell) with 1,2-naphthoquinonediazide sulfonic acid halide, the phenolic compound or the alcoholic compound preferably contains 30 mol% or more and 85 mol% , More preferably 50 mol% or more and 70 mol% or less of 1,2-naphthoquinonediazidesulfonic acid halide. The condensation reaction can be carried out by a known method.

The content of the [G] acid generator is preferably 5 parts by mass or more and 100 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less, and even more preferably 20 parts by mass or more and 40 parts by mass Or less. When the content of the [G] acid generator is within the above range, the difference between the irradiated portion of the irradiated alkali solution and the unexposed portion of the aqueous alkaline solution serving as the developer becomes large, and as a result, the patterning performance becomes good, and the chemical resistance .

<[H] Solvent>

The [H] solvent is used to uniformly dissolve the [A3] polymer, the [G] acid generator, and optional components contained therein if necessary, and does not react with each component. The [H] solvent may be used alone or in combination of two or more.

Examples of the [H] solvent include an alcohol-based solvent, an ether-based solvent, a ketone-based solvent, an amide-based solvent, an ester-based solvent and a hydrocarbon-based solvent.

As the alcohol-based solvent, for example,

As the monoalcohol-based solvent, it is preferable to use at least one solvent selected from the group consisting of methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, Heptanol, sec-heptanol, 3-heptanol, n-octanol, sec-hexanol, sec-hexanol, sec- Sec-octadecyl alcohol, sec-tetradecyl alcohol, sec-tetradecyl alcohol, sec-octadecanol, sec-octadecyl alcohol, Heptadecyl alcohol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol and the like;

Examples of polyhydric alcohol solvents include polyhydric alcohols such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl- , 4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and the like;

Examples of the polyhydric alcohol partial ether solvent include 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- Diethyleneglycol monoethyl ether, diethyleneglycol monopropyl ether, diethyleneglycol monobutyl ether, diethyleneglycol monohexyl ether, propyleneglycol monomethyl ether, propyleneglycol monoethyl ether, diethyleneglycol monomethylether, diethyleneglycol monomethylether, , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether.

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, -Butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, Acetonyl acetone, acetophenone, and the like.

Examples of the amide solvent include N, N'-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, N, Amide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone and the like.

Examples of the ester solvents include methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec- 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate , Methyl acetoacetate, ethyl acetoacetate, acetic acid ethylene glycol monomethyl ether, acetic acid ethylene glycol monoethyl ether, acetic acid ethylene glycol mono-n-propyl ether, acetic acid ethylene glycol mono-n-butyl ether, acetic acid diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl ether acetate, di Propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoacetate acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, Ethyl lactate, ethyl lactate, ethyl lactate, n-butyl lactate, n-butyl lactate, n-butyl methacrylate, - amyl, diethyl malonate, dimethyl phthalate, diethyl phthalate and the like.

As the hydrocarbon-based solvent, for example,

Examples of the aliphatic hydrocarbon solvent include aliphatic hydrocarbons such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, Methylcyclohexane and the like;

Examples of the aromatic hydrocarbon solvents include aliphatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-propylbenzene, n-amylnaphthalene, and the like.

In addition, the [H] solvent may contain a high boiling solvent such as caproic acid, caprylic acid, ethylene carbonate, propylene carbonate and the like together with the above solvent.

<Other optional components>

Examples of other optional components that the positive radiation-sensitive resin composition may contain include cyclic ether compounds other than the [A3] polymer (hereinafter also referred to as "compound X"), antioxidants, surfactants, And the like. The above-mentioned positive radiation-sensitive resin composition may be used alone or in combination of two or more.

[Compound X]

The compound X is a cyclic ether compound other than the [A3] polymer and specifically a compound having a thermal reactive group such as an oxiranyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure). When the positive radiation-sensitive resin composition contains the compound X, heat resistance and surface hardness of the resulting cured film can be improved. As the compound X, a compound having two or more oxiranyl or oxetanyl groups in the molecule is preferable.

As the compound X having two or more oxiranyl groups in the molecule, for example,

Examples of bisphenol diglycidyl ethers include bisphenol diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, Cydyl ether, hydrogenated bisphenol AD diglycidyl ether and the like;

Examples of polyglycidyl ethers of polyhydric alcohols include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether, polyethylene glycol Diglycidyl ether, polypropylene glycol diglycidyl ether and the like;

Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin;

Phenol novolak type epoxy resins;

Cresol novolak type epoxy resin;

Polyphenol type epoxy resins;

Diglycidyl esters of aliphatic long-chain dibasic acids;

Glycidyl esters of higher fatty acids;

Aliphatic polyglycidyl ethers;

Epoxidized soybean oil, and epoxidized linseed oil.

As a commercially available product of the compound X having two or more oxiranyl groups in the molecule, for example,

Epicot 1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 (manufactured by Japan Epoxy Resin Co., Ltd.) as the bisphenol A type epoxy resin;

As the bisphenol F type epoxy resin, Epikote 807 (manufactured by Japan Epoxy Resin Co., Ltd.) and the like;

Examples of the phenol novolak type epoxy resin include Epicote 152, Copper 154 and Copper 157S65 (manufactured by Japan Epoxy Resin Co., Ltd.), EPPN 201 and Copper 202 (manufactured by Nippon Kayaku Co., Ltd.);

EOCN 102, 103S, 104S, 1020, 1025, and 1027 (manufactured by Nippon Kayaku Co., Ltd.), Epikote 180S75 (manufactured by Japan Epoxy Resin Co., Ltd.), and the like as the cresol novolak type epoxy resin;

As the polyphenol type epoxy resin, Epikote 1032H60, XY-4000 (manufactured by Japan Epoxy Resin Co., Ltd.) and the like;

As the cyclic aliphatic epoxy resin, CY-175, Copper 177, Copper 179, Araldite CY-182, Copper 192 and 184 (manufactured by Ciba Specialty Chemicals), ERL-4234, 4299, 4221 and 4206 (Manufactured by Japan Epoxy Resin Co., Ltd.), ED-5661, and EP-5662 (manufactured by Dainippon Ink and Chemicals, Inc.), Shodane 509 (manufactured by Showa Denko K.K.) Manufactured by Celanese Coating), etc .;

Examples of the aliphatic polyglycidyl ether include Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), Epiol TMP (manufactured by Nippon Oil Co., Ltd.) and the like.

Examples of the compound X having two or more oxetanyl groups in the molecule include 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, di [1- (3-ethyl-3-oxetanylmethyl) ether), 3,7-bis (3-oxetanyl) (3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1 - (2-methylethyl) propane di Ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis Ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis Ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethoxy) Ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis Ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentaquis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis Ethyl 3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis 3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl- Oxetanylmethyl) ether, and the like.

Among them, examples of the compound X having two or more oxetanyl groups in the molecule include di [1-ethyl- (3-oxetanyl) methyl] ether, 1,4-bis [ Ethoxy) methyl] benzene.

The content of the compound X is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 1 part by mass or more and 50 parts by mass or less, more preferably 1 part by mass or more and 25 parts by mass or less, based on 100 parts by mass of the polymer [A3] desirable. When the content of the compound X is within the above range, sensitivity, heat resistance and the like can be improved.

[Antioxidant]

The antioxidant is a component capable of decomposing a radical generated by exposure or heating, or a peroxide generated by oxidation, and preventing the dissociation of polymer molecules from dissociation. As a result, the obtained cured film is prevented from deterioration with time of oxidation, and for example, the change in film thickness of the cured film can be suppressed.

Examples of the antioxidant include a compound having a hindered phenol structure, a compound having a hindered amine structure, a compound having an alkyl phosphite structure, and a compound having a thioether structure. Among them, a compound having a hindered phenol structure is preferable as the antioxidant.

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-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5- -Hydroxybenzyl) benzene, N, N'-hexane-1,6-diylbis [3- (3,5- , 5 ', 5'-hexa-tert-butyl-a, a', a'- (mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylene bis (oxyethylene) bis [3- (5-tert- butyl-4-hydroxy-m- tolyl) propionate , Hexamethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris [ Methyl-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -triene, 2,6- Bis (octylthio) -1,3,5-triazin-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 products of the hindered phenol structure include Adekastab AO-20, AO-30, AO-40, AO-50, AO-60, AO- 80, AO-330 (manufactured by ADEKA), sumilizer GM, copper GS, copper MDP-S, copper BBM-S copper WX-R copper GA- (Manufactured by BASF), Yoshinox BHT, and Yoshinox BHT were used in the same manner as in Example 1. The results are shown in Table 1. &lt; tb &gt; &lt; TABLE &gt; Dongbu Corp., Dongbu 2246G, Dongbu 425, Dongbu 250, Dongbu 930, Dongbu SS, Dong TT, Dongbu 917 and Dongbu 314 (manufactured by API Corporation).

Of these, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl- 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and 2,6-di-t-butyl-4-cresol are more preferable.

The content of the antioxidant is preferably 0.001 parts by mass or more and 5 parts by mass or less, more preferably 0.01 parts by mass or more and 2 parts by mass or less, based on 100 parts by mass of the polymer [A3].

[Surfactants]

The surfactant is a component that improves the film formability of the positive radiation-sensitive resin composition. Examples of the surfactant include a fluorine surfactant, a silicone surfactant, and other surfactants.

As the fluorine-based surfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least one of a terminal, a main chain and a side chain is preferable, and for example, a 1,1,2,2-tetrafluoro- (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, hexaethylene glycol di (1,2,2,3,3-hexafluoro-n-pentyl) ether, octaethylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di Hexafluoro-n-pentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, perfluoro- Sodium dodecanesulfonate, 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 Perfluoroalkylpolyoxyethylene, perfluoroalkylpolyoxyethylene, perfluoroalkylpolyoxyethylene, perfluoroalkylpolyoxyethylene, perfluoroalkylalkoxylate, carboxylic acid fluoro, and the like. Alkyl esters and the like.

Examples of commercially available products of the above fluorinated surfactants include BM-1000, BM-1100 (manufactured by BM CHEMIE), Megaface F142D, Copper F172, Copper F173, Copper F183, Copper F178, Copper F191, Copper F471, Copper F476 (Manufactured by Dainippon Ink and Chemicals, Inc.), Fluorad FC-170C, Copper-171, Copper-430, Copper-431 (manufactured by Sumitomo 3M Limited), Surflon S-112, Copper- 103, 104, 105, 106 (manufactured by Asahi Glass), F-top EF301 (manufactured by Asahi Glass Co., Ltd.) , 303 and 352 (manufactured by Shin Akita Kasei), Fotent FT-100, 110, -140, -150, -250, -251, -300, -310, -400S, FTX-218, and -251 (manufactured by NEOS).

Examples of commercially available products of the silicone surfactants include TORAY Silicon DC3PA, Copper DC7PA, Copper SH11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA, Copper SH-190, Copper SH-193, Copper SZ- TSF-4440, TSF-4440, TSF-4445, TSF-4446, TSF-4460 and TSF-4452 GE Toshiba Silicones), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

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

Examples of commercially available products of the above other surfactants include (meth) acrylic acid type copolymer Polyflow No. 57 and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

The content of the surfactant is preferably 0.01 parts by mass or more and 3 parts by mass or less, more preferably 0.05 parts by mass or more and 1 part by mass or less based on 100 parts by mass of the polymer [A3]. When the content of the surfactant is within the above range, the film formability can be effectively improved.

[Adhesion Supplements]

The adhesion assisting agent is a component that improves the adhesiveness between the resulting cured film and the substrate. As the adhesion assisting agent, a functional silane coupling agent having a reactive functional group such as a carboxyl 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,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

The content of the adhesion-promoting agent is preferably 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.1 parts by mass or more and 15 parts by mass or less based on 100 parts by mass of the polymer [A3]. If the amount of the adhesion promoter used exceeds 20 parts by mass, development residue tends to be easily formed.

&Lt; Process for producing positive-tone radiation-sensitive resin composition >

The positive radiation-sensitive resin composition of the present invention is obtained by mixing arbitrary components such as the [A3] polymer, the [G] acid generator, the [H] solvent, the antioxidant, the surfactant, . The positive radiation-sensitive resin composition thus prepared is preferably filtered, for example, with a filter having a pore size of about 0.5 mu m.

&Lt; Process for forming a cured film (3) >

The method (3) for forming a cured film of the present invention comprises:

(1) a step of forming a coating film on a substrate using the positive radiation-sensitive resin composition,

(2) a step of irradiating a part of the coating film with radiation,

(3) a step of developing the coating film irradiated with the radiation, and

(4) a step of heating the developed coating film

Respectively.

According to the method (3) for forming a cured film of the present invention, since the positive-tone radiation-sensitive resin composition has the above-mentioned properties, it is possible to obtain a cured film having good surface hardness and excellent in developing adhesion, heat resistance, chemical resistance, It is possible to form a cured film sufficiently satisfying general characteristics. Each step will be described in detail below.

[Step (C1)]

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

As a coating method, a suitable method such as a spraying method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an ink jet method and the like can be adopted. Of these, spin coating method, bar coating method and slit die coating method are preferable as a coating method. The conditions for the prebaking may vary depending on the kind of each component, the use ratio, and the like, and may be, for example, 60 to 130 DEG C for 30 seconds to 10 minutes. The film thickness of the formed coating film is preferably 0.1 占 퐉 to 8 占 퐉, more preferably 0.1 占 퐉 to 6 占 퐉, and still more preferably 0.1 占 퐉 to 4 占 퐉, as a value after pre-baking.

[Step (C2)]

In this step, a part of the coating film is irradiated with radiation. Specifically, the coating film formed in the step (C1) is irradiated with a radiation through a mask having a predetermined pattern. Examples of the radiation used at this time include ultraviolet rays, deep ultraviolet rays, X-rays, charged particle rays, and the like.

Examples of the ultraviolet ray include g-line (wavelength: 436 nm) and i-line (wavelength: 365 nm). Examples of the far ultraviolet ray include KrF excimer laser light and the like. Examples of X-rays include synchrotron radiation. Examples of the charged particle beam include electron beams and the like. Among these radiation, ultraviolet rays are preferable, and among the ultraviolet rays, radiation including g line, h line and / or i line is more preferable. Examples of radiation exposure dose, 0.1J / m ² to 10,000J / m ² is preferred.

[Step (C3)]

In this step, the coated film irradiated with the radiation is developed. Specifically, in step C2, the coating film irradiated with the radiation is developed with a developer to remove the irradiated portion of the radiation. Examples of the developer include aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, Amine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0 ] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonane, and the like. An aqueous solution containing an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, or a surfactant, or an aqueous alkali solution containing a small amount of various organic solvents capable of dissolving the positive-tone radiation-sensitive resin composition may be used as a developer have.

As the developing method, a suitable method such as a liquid-solid method, a dipping method, a swing dipping method, a shower method and the like can be adopted. The developing time varies depending on the composition of the positive radiation-sensitive resin composition, but may be, for example, 30 seconds to 120 seconds. Further, after the development process, the patterned coating film is subjected to rinsing treatment by water washing, and then irradiated (post-exposure) with radiation by a high-pressure mercury lamp or the like on the entire surface to decompose the [G] acid generator remaining in the coating film . The exposure amount in the subsequent exposure is preferably 2,000 J / m ² to 5,000 J / m ² .

[Step (C4)]

In this step, the developed coating film is heated. Specifically, the coating film is cured by heating and baking (post-baking) the coating film using a heating apparatus such as a hot plate or oven for baking the coated film developed in the step (C3). The calcination temperature in this step is preferably 200 DEG C or less. In addition to the ability to form fine patterns using the radiation-sensitive properties, the method (3) can be suitably used for forming a cured film such as an interlayer insulating film on a plastic substrate of a flexible display. The firing temperature is more preferably 120 deg. C to 180 deg. C, and further preferably 120 deg. C to 150 deg. The firing time varies depending on the type of the heating apparatus, but may be, for example, 5 minutes to 40 minutes in the case of performing heat treatment on a hot plate, 30 minutes to 80 minutes in the case of performing heat treatment in an oven, Is within 30 minutes in the case of performing the heat treatment on the hot plate and within 60 minutes in the case of performing the heat treatment in the oven. In this way, a pattern-like coating film corresponding to a target cured film such as an interlayer insulating film can be formed on the substrate.

&Lt; Cured film (3) >

The cured film (3) of the present invention is formed, for example, by the aforementioned method (3) for forming a cured film by using the above positive radiation-sensitive resin composition. Since the cured film 3 is formed by using the positive radiation-sensitive resin composition, it can have satisfactory surface hardness and can sufficiently satisfy general characteristics such as developing adhesion, heat resistance, chemical resistance, transmittance and relative dielectric constant have.

<Semiconductor device>

The semiconductor device of the present invention includes the above-mentioned cured film (3). Since the semiconductor device includes the cured film 3 formed from the positive radiation-sensitive resin composition, it is possible to improve the degree of integration of the circuit and the recording density, and it is possible to improve the circuit density and the recording density of electronic devices such as display devices, LEDs, Can be preferably used.

<Display element>

The display element of the present invention includes the above semiconductor element. This semiconductor element has a cured film 3 formed from the above positive radiation-sensitive resin composition. Thus, the display device satisfies the general characteristics required for practical use. Examples of the display element include a liquid crystal display element and the like. In the liquid crystal display element, for example, two TFT array substrates each having a liquid crystal alignment film formed on its surface are arranged opposite to each other on the liquid crystal alignment film side through a sealant provided in the peripheral portion of the TFT array substrate. The liquid crystal is filled. The TFT array substrate has wirings arranged in layers, and the wirings are insulated by the cured film such as an interlayer insulating film.

[Example]

Hereinafter, the present invention will be described concretely based on examples, but the present invention is not limited to these examples. The measurement method of each property 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 (manufactured by Showa Denko K.K.)

GPC column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 were combined (manufactured by Shimadzu GLC)

Mobile phase: tetrahydrofuran

Column temperature: 40 DEG C

Flow rate: 1.0 mL / min

Sample concentration: 1.0 mass%

Sample injection amount: 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 providing structural unit (I)] [

The monomeric compounds (1-1) to (1-10) represented by the following formulas (1-1) to (1-10)

[Monomer compound providing structural unit (II-1), structural unit (II-2)] [

(2-1) to (2-7) represented by the following general formulas (2-1) to (2-7)

[Monomer compound providing structural unit (III)] [

(3-1): p-hydroxyphenol methacrylate (4-hydroxyphenyl methacrylate)

(3-2): hydroxyethyl methacrylate (2-hydroxyethyl methacrylate)

(3-3):? -Methyl-p-hydroxystyrene

[Monomer compound providing structural unit (IV)] [

(4-1): methacrylic acid

(4-2): Styrene

(4-3): methyl methacrylate

(4-4): N-Cyclohexylmaleimide

(4-5): Tetrahydrofurfuryl methacrylate

(4-6): Methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl

[Synthesis Example 1] (Synthesis of polymer (A-1)

7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether were fed into a flask equipped with a condenser and a stirrer. Subsequently, 60 parts by mass of the monomer compound (1-1) providing the structural unit (I), 18 parts by mass of the monomer compound (2-1) providing the structural unit (II-1) , 22 parts by mass of the monomer compound (4-2) was charged, the temperature of the solution was raised to 70 占 폚 while slowly stirring with nitrogen substitution, and the polymerization was maintained at this temperature for 4 hours to obtain a polymer solution &Lt; / RTI &gt; The solid concentration of the polymer solution was 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 to 46 Synthesis of Polymers (A-2) to (A-42) and (a-1) to (a-

(A-2) to (A-42) and (a-1) to (a-4) were synthesized in the same manner as in Synthesis Example 1 except that the monomer compounds shown in Table 1 below were used. Respectively. The solid concentration of each polymer solution thus obtained and the Mw and Mw / Mn of each polymer were the same as those of the polymer (A-1). The blank in Table 1 indicates that the corresponding monomer compound was not blended.

&Lt; Production of cured film-forming resin composition (1)

[Example 1]

Diethylene glycol methyl ethyl ether as a solvent was added to a polymer solution containing 100 parts by mass (solid content) of the polymer (A1) as the polymer (A-1) so as to have a solid concentration of 30 mass% To obtain a cured film-forming resin composition (1).

[Example 2 and Comparative Example 1]

The resin composition (1) for forming each of the cured films was produced in the same manner as in Example 1 except that the component [A] was changed to the kind and blending amount shown in Table 2. In Table 2, "-" indicates that the corresponding components are not blended, or that the below-described evaluation is not performed.

&Lt; Preparation of negative-tone radiation-sensitive resin composition (2)

The [B] polymerizable compound, the [C] radiation-sensitive polymerization initiator and the antioxidant [B] used in the preparation of each negative-tone radiation-sensitive 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:? -Carboxy-polycaprolactone monoacrylate (Aronix M-5300 (manufactured by Toagosei Co., Ltd.)

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, Ciba Specialty · Chemicals)

C-2: 1,2-Octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] (Irgacure OXE01, Ciba Specialty Chemicals)

C-3: 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (Irgacure 907, Ciba Specialty Chemicals)

C-4: To a solution of 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin- Produce)

[[D] antioxidant]

D-1: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Adekastab AO-60,

D-2: Tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate (Adekastab AO-

[Example 3]

, 50 parts by mass of (B-1) as the polymerizable compound (B-1), and (C) 100 parts by mass of the (C) radiation- -1) was further mixed with diethyleneglycol methyl ethyl ether as a solvent so as to have a solid content concentration of 30 mass% and then filtered through a membrane filter having a pore size of 0.2 탆 to obtain a negative type radiation sensitive resin composition 2 ).

[Examples 4 to 50 and Comparative Examples 2 to 5]

The same operation as in Example 3 was carried out except that the component [A], the polymerizable compound [B], the radiation-sensitive polymerization initiator [C] and the antioxidant [D] To prepare a radiation-sensitive resin composition (2). In Table 2, "-" indicates that the corresponding components are not blended.

<Evaluation>

Each of the resin compositions (1) and (2) for forming a cured film was evaluated according to the following evaluation method. The evaluation results are shown in Table 2 together.

[Storage stability]

Each resin composition for forming a cured film was allowed to stand in an oven at 40 占 폚 for 1 week, and the viscosity change before and after heating was measured to determine the viscosity change rate (%), which was regarded as an index of storage stability. C: viscosity change rate of 10% or more and less than 15%; D: viscosity change rate of 15% or more; and in the case of A or B, the viscosity change rate is 10% The stability was evaluated as good, and in the case of C or D, it was evaluated as defective. The viscosity was measured at 25 DEG C using an E-type viscometer (VISCONIC ELD. R, manufactured by Toki Sangyo Co., Ltd.).

[Sensitivity]

Using the spinner, each resin composition for forming a cured film was coated on a silicon substrate and then prebaked on a hot plate at 90 캜 for 2 minutes to form a coating film having a film thickness of 3.0 탆. The obtained coating film was irradiated with a predetermined amount of ultraviolet rays through a mercury lamp through a pattern mask having a line-and-space pattern of width 10 mu m. Subsequently, development processing was carried out at 25 DEG C for 60 seconds using a developer containing 2.38% by mass aqueous solution of tetramethylammonium hydroxide, followed by water washing with ultrapure water for 1 minute. At this time, a minimum ultraviolet ray irradiation amount capable of forming a line-and-space pattern having a width of 10 mu m was measured. When the measured value is less than 700 J / m ² , the sensitivity is evaluated as good, and when it is more than 700 J / m ^2,

[Developing adhesion]

Using the spinner, each resin composition for forming a cured film was coated on a silicon substrate and then prebaked on a hot plate at 90 캜 for 2 minutes to form a coating film having a film thickness of 3.0 탆. The resulting 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. Subsequently, development was carried out at 25 DEG C for 60 seconds using a developer containing 2.38% by mass aqueous solution of tetramethylammonium hydroxide, followed by water washing with ultrapure water for 1 minute. The presence or absence of peeling of the line-and-space pattern having a width of 10 mu m was observed with a microscope to obtain a development adhesion. In this case, depending on the degree of peeling, A: no peeling, B: slightly peeling, C: partial peeling, D: full peeling, and in the case of A or B, Defective.

[Chemical resistance]

Using the spinner, each resin composition for forming a cured film was coated on a silicon substrate and then prebaked on a hot plate at 90 캜 for 2 minutes to form a coating film having a film thickness of 3.0 탆. The obtained coating film was irradiated with ultraviolet rays so that the cumulative irradiation amount was 1,000 J / m ² by a mercury lamp. Subsequently, the silicon substrate was heated on a hot plate at 200 DEG C for 30 minutes, and the film thickness (T1) of the cured film thus obtained was measured. The silicon substrate on which the cured film was formed was immersed in dimethylsulfoxide controlled at a temperature of 70 占 폚 for 20 minutes and then the film thickness t1 of the cured film after the immersion was measured to calculate the film thickness change ratio from the following calculation expression, This was used as an indicator of chemical resistance.

Film thickness change rate = {(t1-T1) / T1} x100 (%)

If the absolute value of this value is less than 5%, the chemical resistance is good, and if it is 5% or more, it can be evaluated as bad.

[Heat resistance]

Using the spinner, each resin composition for forming a cured film was coated on a silicon substrate and then prebaked on a hot plate at 90 캜 for 2 minutes to form a coating film having a film thickness of 3.0 탆. The obtained coating film was irradiated with ultraviolet rays so that the cumulative irradiation amount was 1,000 J / m ² by a mercury lamp. Subsequently, this silicon substrate was heated on a hot plate at 200 DEG C for 30 minutes to obtain a cured film. The 5% weight reduction temperature of the obtained cured film was measured under air using a measuring device (TG / DTA220U, manufactured by SII / Nanotechnology) and used as an index of heat resistance. At this time, when the temperature at which the 5% weight loss is 300 ° C or higher, the heat resistance is good, and when the temperature is less than 300 ° C, the heat resistance is bad.

[Transmittance]

Using the spinner, each resin composition for forming a cured film was coated on a glass substrate, and then prebaked on a hot plate at 90 캜 for 2 minutes to form a coating film having a film thickness of 3.0 탆. The obtained coating film was irradiated with ultraviolet rays so that the cumulative irradiation amount was 1,000 J / m ² by a mercury lamp. Subsequently, this glass substrate was heated on a hot plate at 200 DEG 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 Nippon Bunko). In this case, the case where the transmittance of light having a wavelength of 400 nm is 95% or more is evaluated as good (good transparency) and the case of less than 95% is evaluated as bad (poor transparency).

[Surface hardness]

Using the spinner, each resin composition for forming a cured film was coated on a silicon substrate and then prebaked on a hot plate at 90 캜 for 2 minutes to form a coating film having a film thickness of 3.0 탆. The obtained coating film was irradiated with ultraviolet rays so that the cumulative irradiation amount was 1,000 J / m ² by a mercury lamp. Subsequently, this silicon substrate was heated on a hot plate at 200 DEG C for 30 minutes to obtain a cured film. Then, with respect to the substrate on which the cured film was formed, the pencil hardness of the cured film was measured by 8.4.1 pencil scratching test of JIS K-5400-1990, and this was used as an index of surface hardness. When the pencil hardness is 3H or more, it can be judged that the hardness of the surface 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 is defective.

[Relative dielectric constant]

Using the spinner, each resin composition for forming a cured film was coated on an SUS substrate, and then pre-baked on a hot plate at 90 캜 for 2 minutes to form a coating film having a film thickness of 3.0 탆. The above coated film was exposed using an exposure machine (MPA-600FA, manufactured by Canon Inc.) so that the cumulative irradiation amount was 1,000 J / m ² , and the exposed substrate was heated in a clean oven at 200 캜 for 30 minutes to cure Film. Then, a Pt / Pd electrode pattern was formed on the cured film by a vapor deposition method to prepare a sample for measuring the dielectric constant. The substrate having the electrode pattern was measured for CV (relative dielectric constant) at a frequency of 10 kHz using an electrode (HP16451B, manufactured by Yokogawa Hewlett-Packard) and a plasma zone LCR meter (HP4284A, manufactured by Yokogawa Hewlett-Packard) . At this time, a case where the relative dielectric constant is 3.9 or less is evaluated as good, and a case where the relative dielectric constant exceeds 3.9 is evaluated as defective.

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

<Synthesis of [A3] Polymer>

The monomer compounds used in the synthesis of the polymers of Examples and Comparative Examples are shown below.

[Monomer compound providing structural unit (I)] [

The monomeric compounds (1-1) to (1-10) represented by the following formulas (1-1) to (1-10)

[Monomer compound providing structural unit (II-3)] [

(2-1) to (2-7) represented by the following general formulas (2-1) to (2-7)

[Monomer compound providing structural unit (III)] [

(3-1): p-hydroxyphenyl methacrylate (4-hydroxyphenyl methacrylate)

(3-2): hydroxyethyl methacrylate (2-hydroxyethyl methacrylate)

(3-3):? -Methyl-p-hydroxystyrene

[Monomer compound providing structural unit (IV)] [

(4-1): methacrylic acid

(4-2): Styrene

(4-3): methyl methacrylate

(4-4): N-Cyclohexylmaleimide

(4-5): Tetrahydrofurfuryl methacrylate

(4-6): Methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl

[Synthesis Example a1] (Synthesis of polymer (A-a1)

7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether were fed into a flask equipped with a condenser and a stirrer. Subsequently, 60 parts by mass of the compound (1-1) providing the structural unit (I), 18 parts by mass of the compound (2-1) providing the structural unit (II-3) 4-2), and the mixture was purged with nitrogen and slowly stirred, the temperature of the solution was raised to 70 ° C, and the temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer (A-al) . The solid content concentration of the polymer solution was 30.4 mass%, and the copolymer (A-a1) had an Mw of 8,000 and a molecular weight distribution (Mw / Mn) of 2.3.

Synthesis Examples a2 to a45 Synthesis of Polymers (A-a2) to (A-a42) and (a-a1) to (a-a3)

(A-a2) to (A-a42) and (a-a1) to (a-a3) were synthesized in the same manner as in Synthesis Example a1 except that the monomer compounds of the kind and amount shown in Table 3 below were used. Respectively. The solid concentration of each polymer solution thus obtained and the Mw and Mw / Mn of each polymer were the same as those of the polymer (A-a1). Further, the space in Table 3 indicates that the corresponding monomer compound was not blended.

&Lt; Preparation of positive-type radiation-sensitive resin composition >

The [G] acid generator used in the preparation of each positive-tone radiation-sensitive resin composition is shown below.

[G] acid generator

G-1: Trifluoromethanesulfonic acid-1,8-naphthalimide

G-2: 4,4 '- [1- [4- [1- [4-hydroxyphenyl] -1- methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediamine 5-sulfonic acid chloride (2.0 mol)

G-3: A condensate of 1,1,1-tri (p-hydroxyphenyl) ethane and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol)

G-4: Compound represented by the above formula (5-1-i)

[Example a1]

, 30 parts by mass of [G] acid generator (G-2) as an acid generator, 100 parts by mass of (A-a1) as the polymer [A3] 0.5 part by mass of a surfactant (FTX-218, manufactured by Neos Co., Ltd.) and 0.1 part by mass of an antioxidant (IRGANOX1010, manufactured by BASF) were mixed to obtain a solid content concentration of 30 mass% Methyl ethyl ether was further added thereto, followed by filtration through a membrane filter having a pore size of 0.2 탆 to prepare a positive radiation-sensitive resin composition.

[Examples a2 to a58 and Comparative Examples a1 to a6]

Each of the positive-tone radiation-sensitive resin compositions was prepared in the same manner as in Example a1 except that the polymer [A3] and the [G] acid generator were changed to those shown in Table 4.

<Evaluation>

Each of the positive radiation-sensitive resin compositions thus prepared was evaluated according to the following evaluation method. The evaluation results are shown in Table 4 together.

[Storage stability]

Each positive-tone radiation-sensitive resin composition was allowed to stand in an oven at 40 占 폚 for 1 week, and the viscosity before and after heating was measured to determine the rate of change in viscosity (%). C: viscosity change rate of 10% or more and less than 15%; D: viscosity change rate of 15% or more; and in the case of A or B, the viscosity change rate is 10% The stability was evaluated as good, and in the case of C or D, it was evaluated as defective. The viscosity was measured at 25 DEG C using an E-type viscometer (VISCONIC ELD. R, manufactured by Toki Sangyo Co., Ltd.).

[Sensitivity]

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

[Developing adhesion]

Each positive-tone radiation-sensitive resin composition was coated on a silicon substrate using a spinner and prebaked on a hot plate at 90 캜 for 2 minutes to form a coating film having a film thickness of 3.0 탆. The resulting coating film was irradiated with ultraviolet rays of 500 J / m ² by a mercury lamp through a pattern mask having a line-and-space pattern having a width of 10 μm. Subsequently, development was carried out at 25 DEG C for 60 seconds using a developer containing 2.38% by mass aqueous solution of tetramethylammonium hydroxide, followed by water washing with ultrapure water for 1 minute. The presence or absence of peeling of the line-and-space pattern having a width of 10 mu m was observed with a microscope to obtain a development adhesion. In this case, depending on the presence or absence of peeling, A: no peeling, B: slightly peeling, C: partial peeling, D: entire surface peeling, and A or B, Defective.

[Chemical resistance]

Each positive-tone radiation-sensitive resin composition was coated on a silicon substrate using a spinner and prebaked on a hot plate at 90 캜 for 2 minutes to form a coating film having a film thickness of 3.0 탆. The obtained coating film was irradiated with ultraviolet rays so that the cumulative irradiation amount was 3,000 J / m ² by a mercury lamp. Subsequently, the silicon substrate was heated on a hot plate at 200 DEG C for 30 minutes, and the film thickness (T1) of the cured film thus obtained was measured. The silicon substrate on which the cured film was formed was immersed in dimethylsulfoxide controlled at a temperature of 70 캜 for 20 minutes and then the film thickness t 1 of the cured film after the immersion was measured to calculate the film thickness change rate from the following calculation expression As an index of chemical resistance.

Film thickness change rate = {(t1-T1) / T1} x100 (%)

If the absolute value of this value is less than 5%, the chemical resistance is good, and if it is 5% or more, it can be evaluated as bad.

[Heat resistance]

Each positive-tone radiation-sensitive resin composition was coated on a silicon substrate using a spinner and prebaked on a hot plate at 90 캜 for 2 minutes to form a coating film having a film thickness of 3.0 탆. The obtained coating film was irradiated with ultraviolet rays so that the cumulative irradiation amount was 3,000 J / m ² by a mercury lamp. Subsequently, this silicon substrate was heated on a hot plate at 200 DEG C for 30 minutes to obtain a cured film. The 5% weight reduction temperature of the obtained cured film was measured under air using a measuring device (TG / DTA220U, manufactured by SII / Nanotechnology) and used as an index of heat resistance. At this time, when the temperature at which the 5% weight loss is 300 ° C or higher, the heat resistance is good, and when the temperature is less than 300 ° C, the heat resistance is bad.

[Transmittance]

Each positive-tone radiation-sensitive resin composition was coated on a glass substrate using a spinner and prebaked on a hot plate at 90 캜 for 2 minutes to form a coating film having a film thickness of 3.0 탆. The obtained coating film was irradiated with ultraviolet rays so that the cumulative irradiation amount was 3,000 J / m ² by a mercury lamp. Subsequently, this glass substrate was heated on a hot plate at 200 DEG 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 Nippon Bunko). In this case, the case where the transmittance of light having a wavelength of 400 nm is 95% or more is evaluated as good (good transparency) and the case of less than 95% is evaluated as bad (poor transparency).

[Surface hardness]

Each positive-tone radiation-sensitive resin composition was coated on a silicon substrate using a spinner and prebaked on a hot plate at 90 캜 for 2 minutes to form a coating film having a film thickness of 3.0 탆. The obtained coating film was irradiated with ultraviolet rays so that the cumulative irradiation amount was 3,000 J / m ² by a mercury lamp. Subsequently, this silicon substrate was heated on a hot plate at 200 DEG C for 30 minutes to obtain a cured film. Then, with respect to the substrate on which the cured film was formed, the pencil hardness of the cured film was measured according to 8.4.1 pencil scratching test of JIS K-5400-1990, and this was used as an index of surface hardness. When the pencil hardness is 3H or more, it can be estimated that the surface hardness of the cured film is good (the positive radiation sensitive resin composition has sufficient curability) and when it is 2H or less, it is defective.

[Relative dielectric constant]

Each positive-tone radiation-sensitive resin composition was coated on a SUS substrate using a spinner, and then pre-baked on a hot plate at 90 캜 for 2 minutes to form a coating film having a film thickness of 3.0 탆. The above coating film was exposed using an exposure machine (MPA-600FA, manufactured by Canon Inc.) so that the cumulative irradiation amount was 9,000 J / m ² , and the exposed substrate was heated in a clean oven at 200 캜 for 30 minutes to cure Film. Then, a Pt / Pd electrode pattern was formed on the cured film by a vapor deposition method to prepare a sample for measuring the dielectric constant. The substrate having the electrode pattern was measured for CV (relative dielectric constant) at a frequency of 10 kHz using an electrode (HP16451B, manufactured by Yokogawa Hewlett-Packard) and a plasma zone LCR meter (HP4284A, manufactured by Yokogawa Hewlett-Packard) . At this time, a case where the relative dielectric constant is 3.9 or less is evaluated as good, and a case where the relative dielectric constant exceeds 3.9 is evaluated as defective.

The present invention can provide a cured film which has excellent surface hardness and can sufficiently satisfy general characteristics such as sensitivity, developing adhesion, chemical resistance, heat resistance, transmittance and relative dielectric constant, A thermosetting resin composition, a negative-tone radiation-sensitive resin composition, and a positive-tone radiation-sensitive resin composition. Therefore, it is possible to provide a thermosetting resin composition for forming a cured film, a negative radiation-sensitive resin composition, a positive radiation-sensitive resin composition, a thermosetting resin composition for forming the cured film, a negative radiation- The cured film, the semiconductor element, the display element, and the method of forming the cured film formed from the composition can be suitably used in a manufacturing process of an electronic device such as a flexible display.

Claims (17)

[A1] A resin composition comprising a structural unit (I) comprising at least one member selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2) A thermosetting resin composition for forming a cured film containing a polymer having a unit (II-1).

(In the 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 at least one of R ¹ and R ² has 1 to 4 carbon atoms Of fluorinated alkyl groups,
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, provided that at least one of R ³ and R ⁴ is a halogen atom Or a fluorinated alkyl group having 1 to 4 carbon atoms) The thermosetting resin composition according to claim 1, wherein the crosslinkable group (a1) is at least one selected from the group consisting of an oxiranyl group and an oxetanyl group. [A2] A resin composition comprising a structural unit (I) comprising at least one member selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2) A polymer having a unit (II-2)
[B] a polymerizable compound having an ethylenically unsaturated bond, and
[C] Radiation-sensitive polymerization initiator
Wherein the negative radiation-sensitive resin composition is a negative radiation-sensitive resin composition.

(In the 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 at least one of R ¹ and R ² has 1 to 4 carbon atoms Of fluorinated alkyl groups,
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, provided that at least one of R ³ and R ⁴ is a halogen atom Or a fluorinated alkyl group having 1 to 4 carbon atoms) The negative radiation-sensitive resin composition according to claim 3, wherein the crosslinkable group (a2) is at least one member selected from the group consisting of an oxiranyl group, an oxetanyl group, a cyclic carbonate group and a (meth) acryloyl group. The positive photoresist composition according to claim 3 or 4, wherein the [C] radiation-sensitive radiation polymerization initiator is an oxime ester compound and the content of the oxime ester compound is in a range from 0.1 to 10 parts by mass based on 100 parts by mass of the polymer [A2] Sensitive resin composition. The negative radiation-sensitive resin composition according to claim 3 or 4, further comprising [D] an antioxidant. The negative-tone radiation-sensitive resin composition according to claim 3 or 4, wherein the polymerizable compound [B] has at least one carboxyl group in the same molecule. [A3] A polymer comprising a structural unit (I) comprising at least one member selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2), and a cyclic ether structure or a cyclic carbonate structure A polymer having a structural unit (II-3), and
[G] acid generator
Wherein the positive radiation-sensitive resin composition is a positive radiation-sensitive resin composition.

(In the 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 at least one of R ¹ and R ² has 1 to 4 carbon atoms Of fluorinated alkyl groups,
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, provided that at least one of R ³ and R ⁴ is a halogen atom Or a fluorinated alkyl group having 1 to 4 carbon atoms) The positive radiation-sensitive resin composition according to claim 8, wherein the structural unit (II-3) comprises a cyclic ether structure and the cyclic ether structure is at least one of an oxirane structure and an oxetane structure. (1) a step of forming a coating film on a substrate using the thermosetting resin composition for forming a cured film according to any one of claims 1 to 3, and
(2) a step of heating the coating film
To form a cured film. (1) a step of forming a coating film on the substrate by using the negative radiation-sensitive resin composition according to claim 3 or 4, or the positive-tone radiation-sensitive resin composition according to claim 8 or 9,
(2) a step of irradiating a part of the coating film with radiation,
(3) a step of developing the coating film irradiated with the radiation, and
(4) a step of heating the developed coating film
To form a cured film. A cured film formed from the thermosetting resin composition for forming a cured film according to claim 1 or 2. A cured film formed from the negative radiation-sensitive resin composition according to claim 3 or 4, or the positive radiation-sensitive resin composition according to claim 8 or 9. A semiconductor device comprising the cured film according to claim 12. A semiconductor device comprising the cured film according to claim 13. A display device comprising the semiconductor device according to claim 14. A display device comprising the semiconductor device according to claim 15.