JP6303549B2 - Negative radiation sensitive resin composition, cured film for display element, method for forming cured film for display element, and display element - Google Patents

Description

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

In an electronic component such as a thin film transistor type liquid crystal display element, an interlayer insulating film is generally provided to insulate between wirings arranged in layers, and the upper part of a semiconductor element is flattened in an organic electroluminescence element. A flattening film is provided for stacking the electrode and the light emitting layer on the flattening film.
For example, a thin film transistor type liquid crystal display element is manufactured through a process of forming a transparent electrode film on an interlayer insulating film and further forming a liquid crystal alignment film thereon. For this reason, the interlayer insulating film is exposed to high temperature conditions in the transparent electrode film forming process or exposed to a resist stripping solution used for electrode pattern formation. Solvent properties are required.

A conventional interlayer insulating film for a liquid crystal display element uses a positive radiation-sensitive resin composition using an acid generator such as naphthoquinonediazide from the viewpoint of patterning performance (see JP 2001-354822 A). .
Recently, for the purpose of forming a cured film for a display element with higher sensitivity than a positive radiation-sensitive resin composition using an acid generator such as naphthoquinonediazide, for example, JP-A-2004-4669, A crosslinking agent, an acid generator, and a resin which itself is insoluble or hardly soluble in an alkaline aqueous solution, but has a protecting group that can be cleaved by the action of an acid, and becomes soluble in an alkaline aqueous solution after the protecting group is cleaved. There has been proposed a positive chemically amplified resist composition comprising In addition, JP 2004-264623 A and JP 2008-304902 A disclose a positive-type radiation-sensitive material comprising an acetal structure and / or a ketal structure, a resin containing an epoxy group, and an acid generator. Resin compositions have been proposed.

  The positive radiation sensitive resin composition can form a hole pattern or the like formed in an interlayer insulating film of a display element with high sensitivity. However, for example, in the case of a line pattern or the like, a shape defect (for example, It is regarded as a problem that the lower part of the pattern becomes an overhang shape formed by over-development and the like, and causes poor adhesion on the ITO electrode. In recent years, display devices have been required to have larger screens, higher brightness, thinner thickness, etc. From the viewpoint of reducing process time and cost, high sensitivity and high resolution of negative radiation sensitive resin compositions are required. Is required.

  From such a situation, the negative radiation sensitive resin composition having sufficient resolution and sensitivity, and the poor adhesion on the ITO substrate are improved, and the transmittance, light resistance, voltage holding ratio, and thermal stability of the pattern are improved. Development of an excellent cured film for a display element is desired.

JP 2001-354822 A JP 2004-4669 A JP 2004-264623 A JP 2008-304902 A

  The present invention has been made based on the circumstances as described above, and the object thereof is to improve the adhesion failure in the negative radiation sensitive resin composition having high resolution and high sensitivity, and the ITO substrate, and to transmit the light. It is providing the cured film for display elements which is excellent in a rate, light resistance, a voltage holding rate, and the thermal stability of a pattern.

The invention made to solve the above problems is
[A] Polymer component [B] containing the structural unit (I) containing a phenolic hydroxyl group, the structural unit (II) containing a crosslinkable group, and the structural unit (III) containing a carboxyl group in the same or different polymers This is achieved by a negative radiation-sensitive resin composition containing a nonionic photoacid generator and a [C] acid crosslinking agent.

In the negative radiation sensitive resin composition, the crosslinkable group of the structural unit (II) containing the crosslinkable group [A] is selected from the group consisting of a (meth) acryloyl group, a vinyl group, an oxiranyl group, and an oxetanyl group. A negative radiation-sensitive resin composition, and [B] the nonionic acid generator is at least one selected from a compound having an oxime sulfonate structure and a compound having a naphthalimide structure. It is a type radiation sensitive resin composition.
Fine and elaborate patterns can be easily formed by exposure and development utilizing radiation sensitivity, and sufficient resolution and sensitivity are obtained. In addition, the negative radiation-sensitive resin composition contains at least one selected from a compound having an oxime sulfonate structure and a compound having a naphthalimide structure as a nonionic photoacid generator, whereby transmittance, light resistance A cured film for a display element having excellent properties, voltage holding ratio and the like can be formed.
Furthermore, the negative radiation-sensitive resin composition contains [D] an antioxidant, so that the negative radiation-sensitive resin composition has a cured film for display elements with improved light resistance and heat resistance. Can be formed.

  The negative radiation sensitive resin composition is preferable for forming a cured film for a display element. Moreover, the display element provided with the cured film for display elements formed from the said negative radiation sensitive resin composition and this cured film for display elements is suitably contained in this invention.

The method for forming a cured film for a display element of the present invention is as follows.
(1) A step of forming a coating film on a substrate using the negative radiation sensitive resin composition,
(2) A step of irradiating at least 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.

  According to the forming method of the present invention, a cured film for a display element that is excellent in transmittance, light resistance, voltage holding ratio, thermal stability of a pattern, and the like can be formed.

  The “radiation” in the “negative radiation-sensitive resin composition” referred to in the present specification is a concept including visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams and the like. In the coating film formed from the “negative type radiation sensitive resin composition”, the portion irradiated with the radiation is insolubilized in the alkaline developer. The part not irradiated with radiation is solubilized in the alkaline developer. Thereby, pattern formation becomes possible.

  As described above, the negative radiation-sensitive resin composition of the present invention can easily form a fine and elaborate pattern, and has sufficient resolution and sensitivity. Moreover, the said negative radiation sensitive resin composition can form the cured film for display elements which is excellent in the transmittance | permeability, light resistance, a voltage holding rate, etc. Therefore, the negative radiation sensitive resin composition includes a protective film for a color filter for a display element, a spacer, an interlayer insulating film for an array, a color filter for color separation of a solid-state image sensor, a color filter for an organic electroluminescence display element, It is suitable for color filters for flexible displays such as electronic paper, protective films for touch panels, formation of metal wirings and metal bumps, photofabrication resists used for substrate processing, and the like.

<Negative type radiation sensitive resin composition>
The negative radiation sensitive resin composition of the present invention includes [A] a structural unit (I) containing a phenolic hydroxyl group, a structural unit (II) containing a crosslinkable group, and a carboxyl group in the same or different polymers. A polymer component containing the structural unit (III), [B] a nonionic acid generator, and [C] an acid crosslinking agent are contained.
Moreover, the said negative radiation sensitive resin composition can contain [D] antioxidant as a suitable component. Furthermore, the said negative radiation sensitive resin composition may contain another arbitrary component, unless the effect of this invention is impaired. Hereinafter, each component will be described in detail.
<[A] Polymer component>
[A] In the same or different polymers, it has a structural unit (I) containing a phenolic hydroxyl group, a structural unit (II) containing a crosslinkable group, and a polymer component containing a structural unit (III) containing a carboxyl group. It is an ingredient. [A] Since the polymer component has the above structural unit, the radiation-sensitive resin composition is excellent in sensitivity and can suppress a change in the film thickness of the unexposed portion after the development process or after the post-baking process. . Moreover, the [A] polymer component may have another structural unit in the range which does not impair the effect of this invention. In addition, the [A] polymer component may have 2 or more types of each structural unit.

[A] As an aspect of the polymer component, for example,
(A) an embodiment having the structural unit (I), the structural unit (II), and the structural unit (III) in the same polymer molecule;
(B) two or more kinds of polymers having structural units (I) and (III) in one same polymer molecule, and structural units ( II), and the like. Hereinafter, each structural unit will be described in detail.
[Structural unit (I)]
The structural unit (I) is a structural unit having a structural unit containing a phenolic hydroxyl group. [A] Since the polymer component has the structural unit (I), it becomes a site that reacts with the [C] acid crosslinking agent, and the pattern of the cured film formed from the radiation-sensitive resin composition is highly sensitive. Can be formed.

The structural unit (I) is formed by containing a polymerized unit of a polymerizable unsaturated compound having a phenolic hydroxyl group (hereinafter referred to as “phenolic unsaturated compound”), that is, a unit in which a polymerizable unsaturated bond is cleaved. It is a structural unit. This resin preferably has a polymer unit of an unsubstituted or substituted styrene compound (hereinafter simply referred to as “other styrene compound”), that is, a polymerizable unsaturated bond, in addition to the polymer unit of the phenolic unsaturated compound. Has cleaved repeat units.
Examples of the polymerizable unsaturated compound having a phenolic hydroxyl group include o-vinylphenol, m-vinylphenol, p-vinylphenol, o-isopropenylphenol, m-isopropenylphenol and p-isopropenylphenol. Can do. These phenolic unsaturated compounds can be used alone or in combination of two or more.
Examples of the substituent in other styrene compounds include carbon such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group and t-butyl group. A linear or branched alkyl group of 1 to 4; methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, sec-butoxy group, t-butoxy group And a straight or branched alkoxy group having 1 to 4 carbon atoms such as, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Specific examples of such styrenic compounds include styrene derivatives substituted with an alkyl group such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and pt-butylstyrene. A styrene derivative substituted with an alkoxyl group such as p-methoxystyrene, p-ethoxystyrene, pn-propoxystyrene, pi-propoxystyrene, pn-butoxystyrene, pt-butoxystyrene; Examples thereof include styrene derivatives substituted with a halogen atom such as -fluorostyrene, p-chlorostyrene, and p-bromostyrene. These other styrenic compounds can be used alone or in combination of two or more.
The structural unit (I) in the present invention is, for example,
A monomer in which the hydroxyl group of hydroxystyrene is protected, for example, pt-butoxystyrene, p-acetoxystyrene, p-tetrahydropyranyloxystyrene, etc., and optionally other styrene compounds and / or other unsaturated compounds, After the radical, anion, and cation addition polymerization, an acid catalyst and a basic catalyst are allowed to act to remove the protective group by a hydrolysis reaction. Examples of the acid catalyst used include inorganic acids such as hydrochloric acid and sulfuric acid.

  The structural unit (I) can also be formed by a structural unit represented by the formula (6).

(In the formula (6), X represents a direct bond, —COO— or —CONH—, R ³ represents a direct bond, a methylene group, or an alkylene group having 2 to 6 carbon atoms, and R ⁴ represents a hydrogen atom, carbon An alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen, where n is an integer of 1 to 4.
Specific examples of the monomer capable of forming the structural unit represented by the formula (6) include N- (3,5-dimethyl-4-hydroxybenzyl) (meth) acrylamide, N- (4-hydroxyphenyl). ) (Meth) acrylamide, 4-hydroxybenzyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, p-hydroxystyrene, α-methyl-p-hydroxystyrene, and the like. Among these, 4-hydroxyphenyl (meth) acrylate is particularly preferable from the viewpoint of copolymerization with other monomer components. These may be used alone or in combination.
The content of the structural unit (I) in the present invention is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, particularly preferably based on all structural units constituting the [A] polymer component. 15 to 50 mol%. In this case, if the content of the repeating unit derived from the phenolic unsaturated compound is less than 5 mol%, the dissolution rate in the alkali developer tends to be lowered, and the developability, resolution, etc. tend to be impaired, while 80 mol% is reduced. If it exceeds, swelling with respect to the alkaline developer tends to occur, and the pattern shape may be impaired or a pattern defect may occur.
[Structural unit (II)]
The structural unit (II) contains a crosslinkable group. [A] When the polymer component has the structural unit (II) containing a crosslinkable group, the radiation-sensitive resin composition can be obtained by combining the polymers constituting the [A] polymer component or the [A] polymer component. The strength of the formed cured film can be increased by cross-linking with the polymer constituting the.

  Examples of the crosslinkable group include a group containing a polymerizable carbon-carbon double bond, a group containing a polymerizable carbon-carbon triple bond, an oxiranyl group (1,2-epoxy structure), an oxetanyl group (1,3- Epoxy structure), alkoxymethyl group, formyl group, acetyl group, dialkylaminomethyl group, dimethylolaminomethyl group and the like.

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

As structural unit (II), the structural unit which has an oxiranyl group shows the structural unit obtained by superposing | polymerizing the unsaturated compound which has an oxiranyl group.
Specific examples of the unsaturated compound having an oxiranyl group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic acid. -3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, 3,4-epoxycyclohexylmethyl methacrylate, 3, 4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl Acrylate, α-ethylacrylic acid-6,7-epoxyheptyl, o-bi Le benzyl glycidyl ether, m- vinylbenzyl glycidyl ether, p- vinylbenzyl glycidyl ether, cyclohexyl methacrylate, and the like to the 3,4-epoxy cyclo.

The structural unit having an oxetanyl group indicates a structural unit obtained by polymerizing an unsaturated compound having an oxetanyl group. Examples of the unsaturated compound having an oxetanyl group include 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- ( 2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) -2-ethyloxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -2- Phenyloxetane;
3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -2-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -2 -Methacrylic acid esters such as phenyloxetane.

Among these unsaturated compounds having an oxiranyl group and unsaturated compounds having an oxetanyl group, glycidyl methacrylate, 2-methylglycidyl methacrylate, -6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate, 3- (methacryloyloxymethyl) -3-ethyloxetane is copolymerization reactivity and compression performance of cured film for display element, It is preferable from the viewpoint of improving light resistance.
The structural unit having a (meth) acryloyl group is obtained by reacting the carboxy group in the structural unit (II) with the unsaturated compound having an oxiranyl group described above to form an ester bond. More specifically, for example, it can be formed by reacting a polymer having a carboxy group in the structural unit (II) with a compound such as glycidyl methacrylate or 2-methylglycidyl methacrylate.

  The structural unit having a (meth) acryloyl group can be obtained by reacting a polymer having a hydroxyl group with an unsaturated isocyanate compound.

  Examples of the unsaturated isocyanate compound include (meth) acrylic acid derivatives. Specific examples thereof include 2- (meth) acryloyloxyethyl isocyanate, 4- (meth) acryloyloxybutyl isocyanate, (meth ) 2- (2-isocyanatoethoxy) ethyl acrylate and the like. As these commercially available products, Karenz AOI (manufactured by Showa Denko KK) as a commercial product of 2-acryloyloxyethyl isocyanate, Karenz MOI (manufactured by Showa Denko KK), methacryl as a commercial product of 2-methacryloyloxyethyl isocyanate. As a commercial product of the acid 2- (2-isocyanatoethoxy) ethyl, Karenz MOI-EG (manufactured by Showa Denko KK) can be mentioned.

  Of these unsaturated isocyanate compounds, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 4-methacryloyloxybutyl isocyanate or 2- (2-methacrylic acid) is selected from the viewpoint of reactivity with a polymer having a hydroxyl group. Isocyanatoethoxy) ethyl is preferred. An unsaturated isocyanate compound can be used individually or in mixture of 2 or more types.

  The reaction between the hydroxyl group-containing polymer and the unsaturated isocyanate compound is carried out in the presence of a suitable catalyst as necessary, preferably in a polymer solution containing a polymerization inhibitor, while stirring at room temperature or under heating. This can be carried out by introducing an unsaturated isocyanate compound. Examples of the catalyst include di-n-butyltin (IV) dilaurate; and examples of the polymerization inhibitor include p-methoxyphenol.

  As the monomer that gives the structural unit (II), a monomer containing a (meth) acryloyl group, an oxiranyl group or an oxetanyl group is preferred, a monomer containing an oxiranyl group or an oxetanyl group is more preferred, glycidyl methacrylate, 3-Methacryloyloxymethyl-3-ethyloxetane is preferred.

The content ratio of the structural unit (II) is preferably 0.1 mol% or more and 80 mol% or less, more preferably 1 mol% or more and 60 mol% or less with respect to all the structural units constituting the polymer component [A]. preferable. By making the content rate of structural unit (II) into the said range, the intensity | strength of the cured film formed can be raised effectively.
[Structural unit (III)]
The structural unit (III) is a structural unit having a carboxyl group formed from at least one selected from the group consisting of a structural unit derived from an unsaturated carboxylic acid and a structural unit derived from an unsaturated carboxylic anhydride. . Examples of the compound that gives the structural unit (III) include unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated dicarboxylic acid anhydride, poly [carboxylic acid] mono [(meth) acryloyloxyalkyl] ester, both terminals Examples thereof include mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group, unsaturated polycyclic compounds having a carboxy group, and anhydrides thereof.

  Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like. As an anhydride of unsaturated dicarboxylic acid, the anhydride of the compound illustrated as said dicarboxylic acid etc. are mentioned, for example. Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids include, for example, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], hexane. And hydrophthalic acid mono [2- (methacryloyloxy) ethyl]. Examples of the mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends include ω-carboxypolycaprolactone mono (meth) acrylate.

  Of these, monocarboxylic acid and dicarboxylic acid anhydrides are preferred, and (meth) acrylic acid and maleic anhydride are more preferred from the viewpoints of copolymerization reactivity, solubility in alkaline aqueous solutions, and availability.

As a content rate of structural unit (III), Preferably it is 5 mol%-30 mol% with respect to all the structural units, More preferably, it is 10 mol%-25 mol%. By making the content rate of structural unit (III) 5 mol%-30 mol%, the negative radiation sensitive resin composition which is excellent in the radiation sensitivity while optimizing the solubility with respect to alkaline aqueous solution is obtained.
[Other structural units]
[A] The polymer component can contain a compound that gives other structural units other than the structural unit (I), the structural unit (II), and the structural unit (III). For example, (meth) acrylic acid ester having a hydroxyl group, (meth) acrylic acid chain alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton And the like.

  Examples of the (meth) acrylic acid ester having a hydroxyl group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxyhexyl acrylate, and methacrylic acid. Examples include 2-hydroxyethyl acid, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl methacrylate, and the like.

  Examples of the (meth) acrylic acid chain alkyl ester include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, N-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, acrylic acid Examples include isodecyl, n-lauryl acrylate, tridecyl acrylate, and n-stearyl acrylate.

Examples of the (meth) acrylic acid cyclic alkyl ester include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, and tricyclo [5 methacrylate]. .2.1.0 ^2,6 ] decan-8-yloxyethyl, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate , Tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxyethyl acrylate, isobornyl acrylate, and the like.

  Examples of the (meth) acrylic acid aryl ester include phenyl methacrylate, benzyl methacrylate, phenyl acrylate, and benzyl acrylate.

  Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, N-phenylmaleimide, N-cyclohexylmaleimide, and N-tolyl. Maleimide, N-naphthylmaleimide, N-ethylmaleimide, N-hexylmaleimide, N-benzylmaleimide and the like can be mentioned.

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

Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one, and the like.
<[A] Polymer component synthesis method>
[A] The polymer component can be produced, for example, by polymerizing a monomer corresponding to each predetermined structural unit in a suitable solvent using a radical polymerization initiator. For example, a method of dropping a solution containing a monomer and a radical initiator into a reaction solvent or a solution containing the monomer to cause a polymerization reaction, a solution containing the monomer, and a solution containing the radical initiator Separately, a method of dropping a reaction solvent or a monomer-containing solution into a polymerization reaction, a plurality of types of solutions containing each monomer, and a solution containing a radical initiator, It is preferable to synthesize by a method such as a method of dropping it into a reaction solvent or a solution containing a monomer to cause a polymerization reaction.

  [A] Examples of the solvent used in the polymerization reaction of the polymer component include the solvents exemplified in the section of preparation of the radiation-sensitive resin composition described later.

  As the polymerization initiator used in the polymerization reaction, those generally known as radical polymerization initiators can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis ( 2,4-Dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile), azo compounds such as 2,2′-azobis (methyl 2-methylpropionate); benzoyl Organic peroxides such as peroxide and lauroyl peroxide; hydrogen peroxide and the like.

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

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

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

[A] The molecular weight distribution (Mw / Mn) of the polymer component is preferably 3.0 or less, and more preferably 2.6 or less. [A] By making Mw / Mn of a polymer component 3.0 or less, the developability of the obtained cured film can be improved.
<[B] Nonionic photoacid generator>
[B] The nonionic photoacid generator is a compound that generates an acid upon irradiation with radiation. As the radiation, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used. Since the radiation sensitive resin composition contains [B] a nonionic photoacid generator, the radiation sensitive resin composition can exhibit negative radiation sensitive characteristics and has good sensitivity. Can have.
[B] The content of the nonionic photoacid generator in the radiation-sensitive resin composition is a nonionic photoacid generator (hereinafter referred to as “[B] nonionic light”, which is a compound as described later). It may be in the form of "acid generator"), in the form of a photoacid-generating group incorporated as part of the polymer constituting the polymer component [A], or in both forms.

[B] The nonionic photoacid generator is particularly preferably a compound having an oxime sulfonate structure or a compound having a naphthalimide structure. These [B] nonionic photoacid generators may be used alone or in combination of two or more. Details of the compound having an oxime sulfonate structure and the compound having a naphthalimide structure are described below.
[Compound having oxime sulfonate structure]
As a compound which has an oxime sulfonate structure, the compound containing the structure represented by following formula (1) is preferable.

In the above formula (1), R ¹ is an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 12 carbon atoms, or an aryl having 6 to 20 carbon atoms. Or a group in which some or all of the hydrogen atoms of the alkyl group, alicyclic hydrocarbon group and aryl group are substituted with a substituent.

The alkyl group represented by R ¹ is preferably a linear or branched alkyl group having 1 to 12 carbon atoms. The linear or branched alkyl group having 1 to 12 carbon atoms may be substituted with a substituent. Examples of the substituent include an alkoxy group having 1 to 10 carbon atoms and 7,7-dimethyl- Examples thereof include alicyclic groups containing a bridged alicyclic group such as a 2-oxonorbornyl group. Examples of the fluoroalkyl group having 1 to 12 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoropropyl group.

The alicyclic hydrocarbon group represented by R ¹ is preferably an alicyclic hydrocarbon group having 4 to 12 carbon atoms. The alicyclic hydrocarbon group having 4 to 12 carbon atoms may be substituted with a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom. .

The aryl group represented by R ¹ is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group, a naphthyl group, a tolyl group, or a xylyl group. The aryl group may be substituted with a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

  Examples of the compound containing an oxime sulfonate group represented by the above formula (1) include oxime sulfonate compounds represented by the following formula (1-1), formula (1-2), and formula (1-3). Is mentioned.

In the formulas (1-1), (1-2), and formulas (1-3), R ¹ has the same meaning as the formula (1). In the above formulas (1-1) and (1-2), R ⁵ is an alkyl group having 1 to 12 carbon atoms or a fluoroalkyl group having 1 to 12 carbon atoms.
In formula (1-3), X is an alkyl group, an alkoxy group, or a halogen atom. m is an integer of 0-3. However, when there are a plurality of Xs, the plurality of Xs may be the same or different.

  The alkyl group represented by X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group represented by X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom represented by X is preferably a chlorine atom or a fluorine atom. As m, 0 or 1 is preferable. In the above formula (1-3), a compound in which m is 1, X is a methyl group, and the substitution position of X is ortho is preferable.

  Examples of the oxime sulfonate compound represented by the above formula (1-3) include compounds represented by the following formulas (1-3-1) to (1-3-5).

The compounds represented by the above formulas (1-3-1) to (1-3-5) are 5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5 -Octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-p -Toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (2- (octylsulfonyloxyimino) -2- (4-methoxyphenyl) acetonitrile, commercially available .
[Compound having naphthalimide structure]
The compound having a naphthalimide structure is preferably a compound represented by the following formula.

In the formula ^{(2), R 18} and ^R 21 ^{to R 23} is a hydrogen atom.
One of R ¹⁹ and R ²⁰ is a linear or branched alkoxy group having 4 to 18 carbon atoms, and a methylene group at any position not adjacent to the oxygen atom of the alkoxy group is substituted with a —C (═O) — group. A group interrupted by an —O—C (═O) — bond or —OC (═O) —NH— bond from the side closer to the naphthalene ring, a straight chain having 4 to 18 carbon atoms Or a branched alkylthio group, a group in which a methylene group at any position not adjacent to the sulfur atom of this alkylthio group is substituted with a —C (═O) — group, and the above alkylthio group is —O—C from the side closer to the naphthalene ring It is a group interrupted by a (═O) — bond or —OC (═O) —NH— bond, or a group represented by the following formula (3). However, a part or all of the hydrogen atoms of the alkoxy group and alkylthio group of R ¹⁹ and R ²⁰ may be substituted with an alicyclic hydrocarbon group, a heterocyclic group or a halogen atom. The other of R ¹⁹ and R ²⁰ is a hydrogen atom.

In the formula ^{(3), R 25} is a divalent hydrocarbon group having 1 to 12 carbon atoms. R ²⁶ is an alkanediyl group having 1 to 4 carbon atoms. R ²⁷ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group or heterocyclic group having 3 to 10 carbon atoms. Y ¹ is an oxygen atom or a sulfur atom. Y ² is a single bond or an alkanediyl group having 1 to 4 carbon atoms. g is an integer of 0-5.

R ²⁴ in the above formula (2) is a monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted at least one of a halogen atom and an alkylthio group having 1 to 18 carbon atoms, a halogen atom A linear or branched alkyl group having 1 to 18 carbon atoms which may be substituted at least one of an atom and an alicyclic hydrocarbon group, and 3 to 18 carbon atoms which may be substituted with a halogen atom A monovalent alicyclic hydrocarbon group, a halogen atom, and an aryl group having 6 to 20 carbon atoms which may be substituted at least one of a halogen atom and an alkylthio group having 1 to 18 carbon atoms, a halogen atom and 1 to carbon atoms An arylalkyl group having 7 to 20 carbon atoms which may be substituted on at least one of 18 alkylthio groups, an alkylaryl having 7 to 20 carbon atoms which may be substituted with a halogen atom Group, an aryl group having 7 to 20 carbon atoms substituted with an acyl group, a 10-camphoryl group, or a group represented by the following formula (4).

In the formula (4), ^{Y 3} is a single bond or an alkanediyl group having 1 to 4 carbon atoms.

R ²⁸ is an alkanediyl group having 2 to 6 carbon atoms, a halogenated alkanediyl group having 2 to 6 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms.

R ²⁹ is a single bond, an alkanediyl group having 2 to 6 carbon atoms, a halogenated alkanediyl group having 2 to 6 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms. .

R ³⁰ is a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkyl group having 1 to 18 carbon atoms, or an alicyclic hydrocarbon group having 3 to 12 carbon atoms. , An aryl group having 6 to 20 carbon atoms, a halogenated aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a halogenated arylalkyl group having 7 to 20 carbon atoms. One of h and i is 1 and the other is 0 or 1.

Examples of the linear or branched alkoxy group having 4 to 18 carbon atoms represented by R ¹⁹ or R ²⁰ in the above formula (2) include a butyloxy group, a sec-butyloxy group, a t-butyloxy group, and isobutyl. Oxy group, amyloxy group, isoamyloxy group, t-amyloxy group, hexyloxy group, heptyloxy group, isoheptyloxy group, t-heptyloxy group, octyloxy group, isooctyloxy group, t-octyloxy group, 2 -Ethylhexyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group and the like.

Examples of the linear or branched alkylthio group having 4 to 18 carbon atoms represented by R ¹⁹ or R ²⁰ include, for example, a butylthio group, a sec-butylthio group, a t-butylthio group, an isobutylthio group, an amylthio group, Isoamylthio group, t-amylthio group, hexylthio group, heptylthio group, isoheptylthio group, t-heptylthio group, octylthio group, isooctylthio group, t-octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, undecylthio group And a dodecylthio group.

  Examples of the group in which the methylene group not adjacent to the oxygen atom of the alkoxy group having 4 to 18 carbon atoms in the above formula (2) is substituted with —C (═O) — group include 2-ketobutyl-1-oxy Group, 2-ketopentyl-1-oxy group, 2-ketohexyl-1-oxy group, 2-ketoheptyl-1-oxy group, 2-ketooctyl-1-oxy group, 3-ketobutyl-1-oxy group, 4-ketoamyl -1-oxy group, 5-ketohexyl-1-oxy group, 6-ketoheptyl-1-oxy group, 7-ketooctyl-1-oxy group, 3-methyl-2-ketopentane-4-oxy group, 2-keto- Pentane-4-oxy group, 2-methyl-2-ketopentane-4-oxy group, 3-ketoheptane-5-oxy group, 2-adamantanone-5-oxy group and the like can be mentioned.

  Examples of the group in which the methylene group not adjacent to the sulfur atom of the alkylthio group having 4 to 18 carbon atoms in the formula (2) is substituted with a —C (═O) — group include, for example, 2-ketobutyl-1-thio Group, 2-ketopentyl-1-thio group, 2-ketohexyl-1-thio group, 2-ketoheptyl-1-thio group, 2-ketooctyl-1-thio group, 3-ketobutyl-1-thio group, 4-ketoamyl Examples include a -1-thio group, a 5-ketohexyl-1-thio group, a 6-ketoheptyl-1-thio group, and a 7-ketooctyl-1-thio group.

A group interrupted by an —O—C (═O) — bond or an —OC (═O) —NH— bond from the side closer to the naphthalene ring in the alkoxy group having 4 to 18 carbon atoms in the above formula (2), And a group interrupted by an —O—C (═O) — bond or —OC (═O) —NH— bond from the side closer to the naphthalene ring in the above-mentioned alkylthio group having 4 to 18 carbon atoms is —Y ⁵ — ^{R f -O-C (= O} ) -R g or ^-Y 5 ^-R f OC is ^{(= O) -NH-R g} . Y ⁵ is an oxygen atom or a sulfur atom. R ^f and R ^g are groups capable of forming R ¹⁹ and R ²⁰ in the above formula (2). R ^f is a linear or branched alkylene group. This alkylene group may be substituted with an alicyclic hydrocarbon group, a heterocyclic group or a halogen atom. R ^g is a linear or branched alkyl group. This alkyl group may be substituted with an alicyclic hydrocarbon group, a heterocyclic group or a halogen atom. The total number of carbon atoms in R ^f and ^{R g} is 4 to 18.

  The alkoxy group and the alkylthio group may be substituted with a halogen atom, an alicyclic hydrocarbon group, or a heterocyclic group.

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

  The alicyclic hydrocarbon group and the heterocyclic group may be present in a form substituted with the methylene group in the alkoxy group or the alkylthio group, and are substituted with the proton of the methylene group in the alkoxy group or the alkylthio group. Or may be present at the terminal in the alkoxy group or alkylthio group. The alkoxy group and the alkylthio group also include a group formed by directly bonding a carbon atom constituting the ring structure of an alicyclic hydrocarbon group or a heterocyclic group and an oxygen atom or a sulfur atom.

  Examples of the alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo [2.1.1] hexane, bicyclo [2.2.1] heptane, And groups derived from bicyclo [3.2.1] octane, bicyclo [2.2.2] octane, adamantane, and the like.

  Examples of the heterocyclic group include pyrrole, thiophene, furan, pyran, thiopyran, imidazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, pyrrolidine, pyrazolidine, imidazolidine, isoxazolidine , Isothiazolidine, piperidine, piperazine, morpholine, thiomorpholine, chroman, thiochroman, isochroman, isothiochroman, indoline, benzimidazole, benzoxazole, benzothiazole, benzothiadiazole, benzofuroxane, naphthimidazole, benzotriazole, tetraazaindene A saturated heterocyclic ring (tetrahydrofuran ring) hydrogenated to an unsaturated bond or a conjugated bond present in the heterocyclic compound. ) And a group derived from the compound.

  Examples of the alkoxy group substituted with the alicyclic hydrocarbon group include a cyclopentyloxy group, a methylcyclopentyloxy group, a cyclohexyloxy group, a fluorocyclohexyloxy group, a chlorocyclohexyloxy group, a cyclohexylmethyloxy group, and a methylcyclohexyloxy group. , Norbornyloxy group, ethylcyclohexyloxy group, cyclohexylethyloxy group, dimethylcyclohexyloxy group, methylcyclohexylmethyloxy group, norbornylmethyloxy group, trimethylcyclohexyloxy group, 1-cyclohexylbutyloxy group, adamantyloxy group , Menthyloxy group, n-butylcyclohexyloxy group, tert-butylcyclohexyloxy group, bornyloxy group, isobornyloxy group, methylada Nchiruokishi group, adamantanemethyl group, 4-amyl cyclohexyl group, a cyclohexyl cyclohexyloxy group, adamantylethyl group, dimethyl adamantyl group, and the like.

  Examples of the alkoxy group substituted by the heterocyclic group include a tetrahydrofuranyloxy group, a furfuryloxy group, a tetrahydrofurfuryloxy group, a tetrahydropyranyloxy group, a butyrolactyloxy group, a butyrolactylmethyloxy group, An indoleoxy group may be mentioned.

  Examples of the alkylthio group substituted with the alicyclic hydrocarbon group include a cyclopentylthio group, a cyclohexylthio group, a cyclohexylmethylthio group, a norbornylthio group, and an isonorbornylthio group.

  Examples of the alkylthio group substituted with the heterocyclic group include a furfurylthio group and a tetrahydrofurfurylthio group.

Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms represented by R ²⁵ in the above formula (3) include aliphatic hydrocarbon groups such as alkanediyl group, alkenediyl group, alkynediyl group, and cycloalkanediyl. And an alicyclic hydrocarbon group such as a group, and a group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded. Specific examples of the hydrocarbon group having 1 to 12 carbon atoms include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butylene group, butane-1,3- Diyl group, butane-2,3-diyl group, butane-1,2-diyl group, pentylene group, hexylene group, cyclohexylene group, cyclohexylenemethyl group, heptylene group, octylene group, cyclohexyleneethyl group, methylenecyclohexyl Examples include a silylenemethyl group, a nonylene group, a decylene group, an adamantylene group, a norbornylene group, an isonorbornylene group, a dodecylene group, and an undecylene group.

Examples of the alkanediyl group having 1 to 4 carbon atoms represented by R ²⁶ and Y ² in the above formula (3) include a methylene group, an ethylene group, a propane-1,3-diyl group, and propane-1,2 -Diyl group, butylene group, butane-1,3-diyl group, butane-2,3-diyl group, butane-1,2-diyl group and the like can be mentioned.

Examples of the linear or branched alkyl group having 1 to 4 carbon atoms represented by R ²⁷ in the above formula (3) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, sec- A butyl group, a t-butyl group, an isobutyl group, etc. are mentioned.

Examples of the monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms represented by R ²⁷ in the above formula (3) include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, Cyclooctyl group, cyclodecyl group, bicyclo [2.1.1] hexyl group, bicyclo [2.2.1] heptyl group, bicyclo [3.2.1] octyl group, bicyclo [2.2.2] octyl group And an adamantyl group.

Examples of the monovalent heterocyclic group having 3 to 10 carbon atoms represented by R ²⁷ in the above formula (3) include pyrrole, thiophene, furan, pyran, thiopyran, imidazole, pyrazole, thiazole, isothiazole, and oxazole. , Isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, pyrrolidine, pyrazolidine, imidazolidine, isoxazolidine, isothiazolidine, piperidine, piperazine, morpholine, thiomorpholine, indolizine, indole, indazole, purine, quinolidine, isoquinoline, quinoline, naphthyridine , Phthalazine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, perimidine, phenanthroline, carbazole, thiadiazole, oxadiazole, triazine, triazole , Tetrazole, benzimidazole, benzoxazole, benzothiazole, benzothiadiazole, benzofuroxan, naphthimidazole, benzotriazole, tetraazaindene, saturated heterocyclic compounds hydrogenated to unsaturated bonds or conjugated bonds present in the above heterocyclic compounds A monovalent group obtained by removing a hydrogen atom from a ring (tetrahydrofuran ring, etc.) compound and the like can be mentioned.

Examples of the unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms for R ²⁴ in the above formula (2) include an alkenyl group, an alkyl group, an alicyclic hydrocarbon group, and a methylene group in the alkyl group. A group substituted with a cyclic hydrocarbon group, a group where a hydrogen atom of a methylene group in an alkyl group is substituted with an alicyclic hydrocarbon group, or a group where an alicyclic hydrocarbon is present at the terminal of the alkyl group, etc. Can be mentioned.

  Examples of the alkenyl group include allyl group and 2-methyl-2-propenyl group. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, t-butyl group, isobutyl group, amyl group, isoamyl group, t-amyl group, hexyl group, 2-hexyl group, 3-hexyl group, heptyl group, 2-heptyl group, 3-heptyl group, isoheptyl group, t-heptyl group, octyl group, isooctyl group, t-octyl group, 2-ethylhexyl group, nonyl group, Examples include isononyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group and the like. Examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a bicyclo [2.1.1] hexyl group, and a bicyclo [2 2.1] heptyl group, bicyclo [3.2.1] octyl group, bicyclo [2.2.2] octyl group, adamantyl group and the like.

  As a halogen atom which substitutes the said C1-C18 aliphatic hydrocarbon group, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom etc. are mentioned, for example. Examples of the alkylthio group having 1 to 18 carbon atoms replacing the aliphatic hydrocarbon group include, for example, methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, sec-butylthio group, t-butylthio group, isobutylthio group. Group, amylthio group, isoamylthio group, t-amylthio group, hexylthio group, heptylthio group, isoheptylthio group, t-heptylthio group, octylthio group, isooctylthio group, tertiary octylthio group, 2-ethylhexylthio group, nonylthio group, A decylthio group, an undecylthio group, a dodecylthio group, etc. are mentioned.

  Examples of the C1-C18 aliphatic hydrocarbon group substituted with a halogen atom include a trifluoromethyl group, a pentafluoroethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a heptafluoropropyl group, and a 3-bromo group. Propyl group, nonafluorobutyl group, tridecafluorohexyl group, heptadecafluorooctyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, 1,1-difluoropropyl group, 1,1 , 2,2-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, norbornyl-1,1-difluoroethyl group, norbornyltetra And halogenated alkyl groups such as a fluoroethyl group and an adamantane-1,1,2,2-tetrafluoropropyl group. Examples of the C1-C18 aliphatic hydrocarbon substituted with an alkylthio group include a 2-methylthioethyl group, a 4-methylthiobutyl group, a 4-butylthioethyl group, and the like. Examples of the aliphatic hydrocarbon group having 1 to 18 carbon atoms substituted with an -18 alkylthio group include a 1,1,2,2-tetrafluoro-3-methylthiopropyl group.

Examples of the unsubstituted linear or branched alkyl group having 1 to 18 carbon atoms for R ²⁴ in the above formula (2) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and n. -Pentyl group, n-hexyl group, n-octyl group, i-propyl group, i-butyl group, t-butyl group, neopentyl group and the like.

  Examples of the halogen atom for substituting the alkyl group having 1 to 18 carbon atoms include those similar to the halogen atom for substituting the aliphatic hydrocarbon group having 1 to 18 carbon atoms. Examples of the alicyclic hydrocarbon group that replaces the alkyl group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo [2.1.1] hexane, and bicyclo [2.2. .1] groups derived from heptane, bicyclo [3.2.1] octane, bicyclo [2.2.2] octane, adamantane, and the like.

As the unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms in R ²⁴ in the above formula (2), for example,
A monocyclic cycloalkyl group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a methylcyclohexyl group, an ethylcyclohexyl group;
Monocyclic cycloalkenyl groups such as cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclodecenyl, cyclopentadienyl, cyclohexadienyl, cyclooctadienyl, cyclodecadiene;
Bicyclo [2.2.2] octyl group, tricyclo [5.2.1.0 ^2,6 ] decyl group, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecyl group, norbornyl group, a polycyclic cycloalkyl group such as adamantyl group and the like.

  As a halogen atom which substitutes the said C3-C18 alicyclic hydrocarbon group, the same thing as the halogen atom which substitutes a C1-C18 aliphatic hydrocarbon group is mentioned.

Examples of the unsubstituted aryl group having 6 to 20 carbon atoms in R ²⁴ in the above formula (2) include a phenyl group, a naphthyl group, a 4-vinylphenyl group, and a biphenyl group.

  As the halogen atom and the alkylthio group having 1 to 18 carbon atoms for substituting the aryl group having 6 to 20 carbon atoms, the halogen atom and the alkyl group having 1 to 18 carbon atoms for replacing the aliphatic hydrocarbon group having 1 to 18 carbon atoms. The same thing as an alkylthio group is mentioned.

  Examples of the aryl group having 6 to 20 carbon atoms substituted with a halogen atom include a pentafluorophenyl group, a chlorophenyl group, a dichlorophenyl group, a trichlorophenyl group, a 2,4-bis (trifluoromethyl) phenyl group, and a bromoethylphenyl group. Groups and the like. Examples of the aryl group having 6 to 20 carbon atoms substituted with an alkylthio group having 1 to 18 carbon atoms include, for example, 4-methylthiophenyl group, 4-butylthiophenyl group, 4-octylthiophenyl group, 4-dodecylthiophenyl group Groups and the like. Examples of the aryl group having 6 to 20 carbon atoms substituted with a halogen atom and an alkylthio group having 1 to 18 carbon atoms include, for example, 1,2,5,6-tetrafluoro-4-methylthiophenyl group, 1,2,5. , 6-tetrafluoro-4-butylthiophenyl group, 1,2,5,6-tetrafluoro-4-dodecylthiophenyl group, and the like.

Examples of the unsubstituted arylalkyl group having 7 to 20 carbon atoms in R ²⁴ in the above formula (2) include benzyl group, phenethyl group, 2-phenylpropan-2-yl group, diphenylmethyl group, and triphenylmethyl. Group, styryl group, cinnamyl group and the like.

  As a halogen atom and C1-C18 alkylthio group which substitutes the said C7-20 arylalkyl group, a halogen atom which substitutes the said C1-C18 aliphatic hydrocarbon group, and C1-C18 The same thing as the alkylthio group of is mentioned.

  Examples of the arylalkyl group substituted with a halogen atom include a pentafluorophenylmethyl group, a phenyldifluoromethyl group, a 2-phenyl-tetrafluoroethyl group, a 2- (pentafluorophenyl) ethyl group, and the like. Examples of the arylalkyl group having 7 to 20 carbon atoms substituted with an alkylthio group having 1 to 18 carbon atoms include a p-methylthiobenzyl group. Examples of the arylalkyl group substituted with a halogen atom and an alkylthio group having 1 to 18 carbon atoms include a 2,3,5,6-tetrafluoro-4-methylthiophenylethyl group.

Examples of the unsubstituted alkylaryl group having 7 to 20 carbon atoms in R ²⁴ in the above formula (2) include a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, and a 3-isopropylphenyl group. 4-isopropylphenyl group, 4-butylphenyl group, 4-isobutylphenyl group, 4-t-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, 4-octylphenyl group, 4- (2- Ethylhexyl) phenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethyl Phenyl, 2,4-di-t-butylphenyl, 2,5-di-tert-butylphenyl, 2,6-di-t-butylphenyl group, 2, 4-di-t-pentylphenyl group, 2,5-di-t-amylphenyl group, 2,5-di-t-octylphenyl group, cyclohexylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6 -Trimethylphenyl group, 2,4,6-triisopropylphenyl group and the like.

Examples of the unsubstituted aryl group having 7 to 20 carbon atoms in R ²⁴ in the above formula (2) include a naphthyl group and a biphenyl group.
Is mentioned.

  Examples of the acyl group that substitutes for the aryl group having 7 to 20 carbon atoms include a methanoyl group, an ethanoyl group, a propanoyl group, a benzoyl group, and a propenoyl group.

  Examples of the aryl group having 7 to 20 carbon atoms substituted with an acyl group include an acetylphenyl group, an acetylnaphthyl group, a benzoylphenyl group, a 1-anthraquinolyl group, and a 2-anthraquinolyl group.

10-camphorsulfonic yl group represented by R ²⁴ in the formula (2) are those represented by the following formula.

Examples of the alkanediyl group having 1 to 4 carbon atoms represented by Y ³ in the above formula (4) include a methylene group, an ethylene group, a propane-1,3-diyl group, and a propane-1,2-diyl group. , Butylene group, butane-1,3-diyl group, butane-2,3-diyl group, butane-1,2-diyl group, and the like.

Examples of the alkanediyl group having 2 to 8 carbon atoms represented by R ²⁸ or R ²⁹ in the above formula (4) include, for example, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, isopropylene. Group, isobutylene group, 2-methyltrimethylene group, isopentylene group, isohexylene group, isooctylene group, 2-ethylhexylene group and the like. Examples include groups in which at least one hydrogen atom in the alkanediyl group having 2 to 8 carbon atoms is substituted with a halogen atom. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom.

Examples of the halogenated alkanediyl group having 2 to 6 carbon atoms represented by R ²⁸ or R ²⁹ in the above formula (4) include, for example, a tetrafluoroethylene group, a 1,1-difluoroethylene group, and a 1-fluoroethylene group. 1,2-difluoroethylene group, hexafluoropropane-1,3-diyl group, 1,1,2,2-tetrafluoropropane-1,3-diyl group, 1,1,2,2-tetrafluoropentane A -1,5-diyl group is exemplified.

Examples of the arylene group having 6 to 20 carbon atoms represented by R ²⁸ or R ²⁹ in the above formula (4) include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 2,5-dimethyl-1,4-phenylene group, 4,4′-biphenylene group, diphenylmethane-4,4′-diyl group, 2,2-diphenylpropane-4,4′-diyl group, naphthalene-1, 2-diyl group, naphthalene-1,3-diyl group, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-1,6-diyl group, naphthalene-1,7-diyl, naphthalene -1,8-diyl group, naphthalene-2,3-diyl group, naphthalene-2,6-diyl group, naphthalene-2,7-diyl group and the like.

In the halogenated arylene group having 6 to 20 carbon atoms represented by R ²⁸ or R ²⁹ in the above formula (4), at least one hydrogen atom in the arylene group having 6 to 20 carbon atoms is substituted with a halogen atom. Group, for example, tetrafluorophenylene group and the like.

Examples of the linear or branched alkyl group having 1 to 18 carbon atoms represented by R ³⁰ in the above formula (4) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, sec- Butyl group, t-butyl group, isobutyl group, amyl group, isoamyl group, t-amyl group, hexyl group, 2-hexyl group, 3-hexyl group, heptyl group, 2-heptyl group, 3-heptyl group, isoheptyl group , T-heptyl group, octyl group, isooctyl group, t-octyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, dodecyl group and the like.

Examples of the linear or branched alkyl halide group having 1 to 18 carbon atoms represented by R ³⁰ in the above formula (4) include, for example, at least one hydrogen in the alkyl group having 1 to 18 carbon atoms. A group in which an atom is substituted with a halogen atom is exemplified. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. Examples of the halogenated alkyl group having 1 to 18 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, a tridecafluorohexyl group, a heptadecafluorooctyl group, 2, 2,2-trifluoroethyl group, 1,1-difluoroethyl group, 1,1-difluoropropyl group, 1,1,2,2-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 2 , 2,3,3,3-pentafluoropropyl group, 1,1,2,2-tetrafluorotetradecyl group and the like.

Examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms represented by R ³⁰ in the above formula (4) include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. , Cyclodecyl group, bicyclo [2.1.1] hexyl group, bicyclo [2.2.1] heptyl group, bicyclo [3.2.1] octyl group, bicyclo [2.2.2] octyl group, adamantyl group Etc.

The aryl group having 6 to 20 carbon atoms, the halogenated aryl group having 6 to 20 carbon atoms, the arylalkyl group having 7 to 20 carbon atoms, and the 7 to 20 carbon atoms represented by R ³⁰ in the above formula (2). Examples of the halogenated arylalkyl group include those similar to R ²⁴ in the above formula (4).

  [B] As content of a nonionic photo-acid generator, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] polymer components, and 1 mass part-5 mass parts are more. preferable. [B] By setting the content of the nonionic photoacid generator in the above range, the radiation sensitivity of the radiation-sensitive resin composition can be optimized, and a cured film having high surface hardness can be formed while maintaining transparency. .

[B] As content of a nonionic photo-acid generator, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] polymer components, and 1 mass part-5 mass parts are more. preferable. [B] By setting the content of the nonionic photoacid generator in the above range, the sensitivity of the radiation-sensitive resin composition can be optimized, and a cured film having high surface hardness can be formed while maintaining transparency.
<[C] acid crosslinking agent>
In the present invention, the [C] acid crosslinking agent is capable of inhibiting the solubility in an alkaline developer by crosslinking with the phenolic hydroxyl group in the [A] polymer component in the presence of an acid, for example, an acid generated by exposure. There is no particular limitation on the type.
As a [C] acid crosslinking agent in this invention, the compound which has a structure shown by following formula (5) is preferable.

(In Formula (5), R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. M is an integer of 1 to 3.)
Examples of the compound having a structure represented by the following formula (5) include:
N- (alkoxymethyl) glycoluril compound represented by the following formula (7),
N- (alkoxymethyl) urea compound represented by the following formula (8):
N- (alkoxymethyl) melamine compound represented by the following formula (9),
Examples thereof include N- (alkoxymethyl) amino compounds such as N- (alkoxymethyl) ethyleneurea compounds represented by the following formula (10).

In the formula (7), m and R ² have the same definition as in the formula (5), R ² independently represents an alkyl group having 1 to 6 carbon atoms, and m represents an integer of 1 to 3.
Specific examples of the N- (alkoxymethyl) glycoluril compound represented by the formula (7) include N, N, N, N-tetra (methoxymethyl) glycoluril, N, N, N, N-tetra (ethoxy). Methyl) glycoluril, N, N, N, N-tetra (n-propoxymethyl) glycoluril, N, N, N, N-tetra (i-propoxymethyl) glycoluril, N, N, N, N-tetra (N-Butoxymethyl) glycoluril, N, N, N, N-tetra (t-butoxymethyl) glycoluril and the like can be mentioned.

In Formula (8), m and R ² have the same definition as in Formula (5), R ² independently represents an alkyl group having 1 to 6 carbon atoms, and m represents an integer of 1 to 3.
Specific examples of the N- (alkoxymethyl) urea compound represented by the formula (8) include N, N-di (methoxymethyl) urea, N, N-di (ethoxymethyl) urea, N, N-di ( n-propoxymethyl) urea, N, N-di (i-propoxymethyl) urea, N, N-di (n-butoxymethyl) urea, N, N-di (t-butoxymethyl) urea and the like. it can.

In formula (9), m and R ² have the same definition as in formula (5), R ² independently represents an alkyl group having 1 to 6 carbon atoms, and m represents an integer of 1 to 3.
Specific examples of the N- (alkoxymethyl) melamine compound represented by the formula (9) include N, N, N, N, N, N-hexa (methoxymethyl) melamine, N, N, N, N, N N-hexa (ethoxymethyl) melamine, N, N, N, N, N, N-hexa (n-propoxymethyl) melamine, N, N, N, N, N, N-hexa (i-propoxymethyl) Mention may be made of melamine, N, N, N, N, N, N-hexa (n-butoxymethyl) melamine, N, N, N, N, N, N-hexa (t-butoxymethyl) melamine and the like.

In the formula (10), m and R ² have the same definition as in the formula (5), R ² independently represents an alkyl group having 1 to 6 carbon atoms, and m represents an integer of 1 to 3.
Specific examples of the N- (alkoxymethyl) ethyleneurea compound represented by the formula (10) include N, N-di (methoxymethyl) -4,5-di (methoxymethyl) ethyleneurea, N, N-di (Ethoxymethyl) -4,5-di (ethoxymethyl) ethyleneurea, N, N-di (n-propoxymethyl) -4,5-di (n-propoxymethyl) ethyleneurea, N, N-di (i -Propoxymethyl) -4,5-di (i-propoxymethylmethyl) ethyleneurea, N, N-di (n-butoxymethyl) -4,5-di (n-butoxymethyl) ethyleneurea, N, N- Examples thereof include di (t-butoxymethyl) -4,5-di (t-butoxymethylmethyl) ethylene urea.
In the present invention, the [C] acid crosslinking agent may be used alone or in combination of two or more. In the present invention, the amount of the [C] acid crosslinking agent used is preferably 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass, and still more preferably, per 100 parts by mass of the [A] polymer component. 2 to 20 parts by mass. [C] When the blending amount of the acid crosslinking agent is less than 0.5 parts by mass, the effect of inhibiting the solubility of the polymer component in the alkaline developer is small, the remaining film ratio is lowered, the pattern is swollen or meandered On the other hand, if it exceeds 50 parts by mass, the heat resistance as a cured film tends to be reduced.
<[D] Antioxidant>
[D] An antioxidant is a component that suppresses the cleavage of the bond of polymer molecules by capturing radicals generated by exposure or heating or by decomposing a peroxide generated by oxidation. When the radiation sensitive resin composition contains the [D] antioxidant, the degradation degradation of the polymer molecules in the formed cured film is suppressed, and for example, light resistance and the like can be improved. In addition, you may use [D] antioxidant individually or in combination of 2 or more types.

  [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 these, it is preferable that [D] antioxidant has a hindered phenol structure. [D] When the antioxidant has a hindered phenol structure, the degradation degradation of the polymer molecules in the formed cured film can be further suppressed.

  Examples of the compound having a hindered phenol structure include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene bis [3- (3,5-dithione). -Tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tris- (3,5-di-tert-butyl-4- Hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N′-hexane-1, 6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide) 3,3 ′, 3 ′, 5 ′, 5′-hexa-tert-butyl-a, a ′, a ′-(mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (Octylthiomethyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) Propionate, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6- Xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio)- 1,3 5-triazin-2-ylamine) phenol, and the like.

  Examples of commercially available compounds having the hindered phenol structure include, for example, ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80. , AO-330 (above, manufactured by ADEKA), SumilizerGM, GS, MDP-S, BBM-S, WX-R, GA-80 (above, manufactured by Sumitomo Chemical), IRGANOX1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 565, IRGAMOD295 (above, manufactured by BASF).

  [D] As an antioxidant, among compounds having a hindered phenol structure, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris- (3,5 -Di-tert-butyl-4-hydroxybenzyl) -isocyanurate is more preferred.

[D] The content of the antioxidant is preferably 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 0.2 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the polymer component [A]. preferable. [D] By making content of antioxidant into the said range, the cleavage degradation of the cured film formed can be suppressed effectively.
<Other optional components>
In addition to the components [A] to [D], the radiation sensitive resin composition includes [E] a basic compound, [F] a surfactant, and [A] as long as the effects of the present invention are not impaired. G] Other optional components such as an adhesion aid may be contained. Each other optional component may be used alone or in combination of two or more. Hereinafter, each component will be described in detail.
<[E] basic compound>
[E] The basic compound may be arbitrarily selected from those used in chemically amplified resists. For example, aliphatic amine, aromatic amine, heterocyclic amine, quaternary ammonium hydroxide, carboxylic acid quaternary An ammonium salt etc. are mentioned. When the radiation sensitive resin composition contains the [E] basic compound, the diffusion length of the acid generated from the nonionic photoacid generator [B] by exposure can be appropriately controlled, and pattern development Can be improved.

  Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and dicyclohexyl. Examples include amines and dicyclohexylmethylamine.

  Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.

  Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, and N-methyl-4-phenylpyridine. , 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine , Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4,3,0] -5-nonene, 1,8-diazabicyclo [5,3,0]- 7-undecene etc. are mentioned.

  Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.

  Examples of the carboxylic acid quaternary ammonium salt include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

  Among these, the [E] basic compound is preferably a heterocyclic amine, such as 4-dimethylaminopyridine, 4-methylimidazole, 1,5-diazabicyclo [4,3,0] -5-nonene, dimethyl. n-dodecylamine, triphenylsulfonium salicylate, 2-phenylbenzimidazole and the like are more preferable.

[E] The content of the basic compound is preferably 0.001 part by mass or more and 1 part by mass or less, and 0.005 part by mass or more and 0.2 part by mass or less with respect to 100 parts by mass of the polymer component [A]. Is more preferable. [E] By making content of a basic compound into the said range, pattern developability improves more.
<[F] Surfactant>
[F] Surfactant is a component which improves the film-forming property of the said radiation sensitive resin composition. Examples of [F] surfactants include fluorine-based surfactants and silicone-based surfactants. When the radiation sensitive resin composition contains the [F] surfactant, the surface smoothness of the coating film can be improved, and as a result, the film thickness uniformity of the formed cured film can be further improved.

  As the fluorosurfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least one of the terminal, main chain and side chain is preferable.

  Examples of commercially available fluorosurfactants include BM-1000, BM-1100 (manufactured by BM CHEMIE), MegaFuck F142D, F172, F173, F183, F178, F191, F191, and F471. , F476 (above, manufactured by Dainippon Ink and Chemicals), Fluorard FC-170C, FC-171, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Footent FT-100, FT- 110, FT-140A, FT-150, FT-250, FT-251, FT-300, FT-310, FT-400S, FTX-218, FT-251 (and above, Neos) Manufactured) and the like.

  Examples of commercially available silicone surfactants include Toray Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, and SZ-6032. SF-8428, DC-57, DC-190, SH 8400 FLUID (above, manufactured by Toray Dow Corning Silicone), and the like.

[F] The content of the surfactant is preferably 0.01 parts by mass or more and 2 parts by mass or less, and more preferably 0.05 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass of the polymer component [A]. preferable. [F] By making content of surfactant into the said range, the film thickness uniformity of the coating film formed can be improved more.
<[G] Adhesion aid>
[G] The adhesion assistant is a component that improves the adhesion between a cured film and an inorganic substance that serves as a substrate, for example, a silicone compound such as silicone, silicone oxide, or silicon nitride, or a metal such as gold, copper, or aluminum. [G] As the adhesion assistant, a functional silane coupling agent is preferable. As said functional silane coupling agent, the silane coupling agent etc. which have reactive substituents, such as a carboxy group, a methacryloyl group, an isocyanate group, an epoxy group (preferably oxiranyl group), a thiol group, etc. are mentioned, for example.

  Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and γ-glycidoxy. Examples include propyltrimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. . Among these, as the functional silane coupling agent, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-Methacryloxypropyltrimethoxysilane is preferred.

[G] The content of the adhesion assistant is preferably 0.5 parts by mass or more and 20 parts by mass or less, and more preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymer component [A]. [G] By setting the content of the adhesion assistant in the above range, the adhesion between the formed cured film and the substrate is further improved.
<Method for preparing radiation-sensitive resin composition>
The said radiation sensitive resin composition mixes a [A] polymer, a [B] nonionic photoacid generator, a [C] acid crosslinking agent, a suitable component as needed, and other arbitrary components with a solvent. Prepared in a dissolved or dispersed state. For example, the said radiation sensitive resin composition can be prepared by mixing each component in a predetermined ratio in a solvent.

  As the solvent, a solvent in which each component is uniformly dissolved or dispersed and does not react with each component is preferably used. Examples of the solvent include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, and aromatics. Examples include hydrocarbons, ketones, and other esters.

  Examples of the alcohols include methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, and 3-phenyl-1-propanol.

  Examples of the ethers include tetrahydrofuran.

  Examples of the glycol ether include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether.

  Examples of the ethylene glycol alkyl ether acetate include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate.

  Examples of the diethylene glycol alkyl ether include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether.

  Examples of the propylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like.

  Examples of the propylene glycol monoalkyl ether acetate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate and the like.

  Examples of the propylene glycol monoalkyl ether propionate include propylene monoglycol methyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, and propylene glycol monobutyl ether propionate. Can be mentioned.

  Examples of the aromatic hydrocarbons include toluene and xylene.

  Examples of the ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and the like.

  Examples of the other esters include butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, Butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy-3- Methyl methyl butanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, propoxy Ethyl acetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2- Examples include ethyl ethoxypropionate, propyl 2-ethoxypropionate, and butyl 2-ethoxypropionate.

Among these solvents, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate and butyl methoxyacetate are preferred, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, Propylene glycol monomethyl ether and butyl methoxyacetate are more preferable, and diethylene glycol ethyl methyl ether is more preferable.
<Method for forming cured film>
The said radiation sensitive resin composition can be used suitably for formation of a cured film.

The method for forming the cured film of the present invention is as follows.
(1) The process of forming a coating film on a board | substrate using the said radiation sensitive resin composition,
(2) A step of irradiating at least 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.

According to the forming method, a cured film having high pattern shape stability can be formed. Further, since the amount of change in the film thickness of the unexposed portion can be suppressed, the production process margin can be improved as a result, and the yield can be improved. Furthermore, a cured film having a fine and elaborate pattern can be easily formed by forming a pattern by exposure, development and heating utilizing photosensitivity.
[Step (1)]
In this step, the radiation-sensitive resin composition is used and applied onto a substrate to form a coating film. Preferably, the solvent is removed by prebaking the coated surface.

Examples of the substrate include glass, quartz, silicone, and resin. Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, a ring-opening polymer of cyclic olefin, and a hydrogenated product thereof. As prebaking conditions, although it changes also with kinds, compounding ratios, etc. of each component, it can be set as 70 degreeC-120 degreeC, about 1 minute-10 minutes.
[Step (2)]
In this step, at least a part of the formed coating film is exposed to radiation and exposed. When exposing, it exposes normally through the photomask which has a predetermined pattern. As the radiation used for exposure, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation containing ultraviolet light of 365 nm is more preferable. Energy of exposure intensity at the wavelength 365nm radiation, by the value measured by luminometer (OAI model356, OAI Optical Ltd. ^Associates), is preferably ^{500J / m 2 ~6,000J / m 2} , 1,500J / m 2 ˜1,800 J / m ² is more preferable.
[Step (3)]
In this step, the coating film irradiated with the radiation is developed. By developing the coated film after exposure, unnecessary portions (radiation irradiated portions) are removed to form a predetermined pattern. As the developer used in this development step, an alkaline aqueous solution is preferable. Examples of the alkali include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and ketones. Examples thereof include organic solvents and alcohol-based organic solvents.

  An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, or a surfactant can be added to the alkaline aqueous solution. The alkali concentration in the aqueous alkali solution is preferably from 0.1% by mass to 5% by mass from the viewpoint of obtaining appropriate developability. Examples of the developing method include a liquid piling method, a dipping method, a rocking dipping method, a shower method, and the like. The development time varies depending on the composition of the radiation sensitive resin composition, but is about 10 seconds to 180 seconds. Subsequent to such development processing, for example, washing with running water is performed for 30 seconds to 90 seconds, and then a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen.

Thickness change rate of the thickness T ₁ of the after development with respect to the film thickness T ₀ of the coating film before development is preferably 90% or more. As described above, according to the forming method using the radiation-sensitive resin composition, the amount of change in the film thickness of the unexposed portion with respect to the development time can be suppressed, and the film thickness after development is 90% of the film thickness before development. % Or more can be maintained.
[Step (4)]
In this step, the developed coating film is heated. For heating, the patterned thin film is heated using a heating device such as a hot plate or an oven, whereby the curing reaction of the polymer component [A] can be promoted to form a cured film. As heating temperature, it is about 120 to 250 degreeC, for example. The heating time varies depending on the type of the heating device, but is, for example, about 5 to 30 minutes for a hot plate and about 30 to 90 minutes for an oven. Moreover, the step baking method etc. which perform a heating process 2 times or more can also be used. In this way, a patterned thin film corresponding to the desired cured film can be formed on the surface of the substrate. The film thickness of the formed cured film is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm.
<Curing film>
The cured film of the present invention is formed from the radiation sensitive resin composition. Since the said cured film is formed from the said radiation sensitive resin composition, it has high surface hardness, heat resistance, etc., and there are few changes of a film thickness. Since the cured film has the above properties, it is suitable as, for example, an interlayer insulating film of a display element, a spacer, a protective film, a color filter coloring pattern, or the like. In addition, although it does not specifically limit as a formation method of the said cured film, It is preferable to use the formation method of the said cured film mentioned above.
<Display element>
The display element of the present invention includes the cured film. The display element includes, for example, a liquid crystal cell, a polarizing plate, and the like which will be described later. Since the display element includes the cured film, the display element is excellent in reliability such as heat resistance.

  As a method for manufacturing the display element, first, a pair (two) of transparent substrates having a transparent conductive film (electrode) on one side is prepared, and the radiation-sensitive resin composition is formed on the transparent conductive film of one of the substrates. Using an object, an interlayer insulating film, a spacer, a protective film, or both are formed according to the method for forming a cured film described above. Next, an alignment film having liquid crystal alignment ability is formed on the transparent conductive film and the spacer or protective film of these substrates. These substrates are arranged facing each other with a certain gap (cell gap) so that the liquid crystal alignment direction of each alignment film is orthogonal or antiparallel, with the surface on which the alignment film is formed inside. A liquid crystal is filled in the cell gap defined by the surface of the substrate (alignment film) and the spacer, and the filling hole is sealed to constitute a liquid crystal cell. Then, the display element of the present invention is bonded to both outer surfaces of the liquid crystal cell such that the polarizing direction is aligned or orthogonal to the liquid crystal alignment direction of the alignment film formed on one surface of the substrate. can get.

  As another method for manufacturing a display element, a pair of transparent substrates on which a transparent conductive film, an interlayer insulating film, a protective film, a spacer, or both, and an alignment film are formed are prepared in the same manner as the above manufacturing method. After that, along the edge of one of the substrates, an ultraviolet curable sealant is applied using a dispenser, then the liquid crystal is dropped into a fine droplet using a liquid crystal dispenser, and the two substrates are bonded together under vacuum. Do. Then, both the substrates are sealed by irradiating the sealing agent part with ultraviolet rays using a high-pressure mercury lamp. Finally, the display element of the present invention is obtained by attaching polarizing plates to both outer surfaces of the liquid crystal cell.

  Examples of the liquid crystal used in the above-described manufacturing method of each display element include nematic liquid crystal and smectic liquid crystal. In addition, as a polarizing plate used outside the liquid crystal cell, a polarizing film in which a polarizing film called an “H film” that absorbs iodine while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films, or an H film Examples thereof include a polarizing plate made of itself.

  In the organic EL display element, the cured film formed from the radiation-sensitive resin composition can be used as a planarizing film formed on the TFT element, a partition material that separates light emitting sites, and the like.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. The measuring method of each physical property value is shown below.
[Weight average molecular weight (Mw) and number average molecular weight (Mn)]
It measured by gel permeation chromatography (GPC) under the following conditions. The degree of dispersion (Mw / Mn) was calculated from the measurement results of Mw and Mn.

Apparatus: GPC-101 (made by Showa Denko)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined Mobile phase: Tetrahydrofuran Column temperature: 40 ° C
Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene <Synthesis of [A] component>
[Synthesis Example 1] (Synthesis of polymer (A-1))
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 15 parts by mass of methacrylic acid, 35 parts by mass of p-hydroxystyrene, 10 parts by mass of styrene, and 40 parts by mass of 3-methacryloyloxymethyl-3-ethyloxetane were charged and purged with nitrogen, and then gently stirring was started. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-1). The weight average molecular weight (Mw) in terms of polystyrene of the polymer (A-1) was 8,500. Moreover, the solid content concentration of the polymer solution obtained here was 31.6 mass%.
[Synthesis Example 2] (Synthesis of polymer (A-2))
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 15 parts by weight of methacrylic acid, 40 parts by weight of 4-hydroxyphenyl methacrylate, 40 parts by weight of glycidyl methacrylate, and 5 parts by weight of hydroxyethyl methacrylate were charged with nitrogen, and then gently stirred. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-2). The polymer (A-2) had a polystyrene equivalent weight average molecular weight (Mw) of 11,000. Moreover, the solid content concentration of the polymer solution obtained here was 32.7 mass%.
[Synthesis Example 3] (Synthesis of Polymer (A-3))
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate. Subsequently, 15 parts by mass of methacrylic acid, 15 parts by mass of p-hydroxystyrene, 20 parts by mass of 4-hydroxyphenyl methacrylate, 40 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate, and 10 parts by mass of styrene were charged, and after the nitrogen substitution, Stirring was started. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-3). The polymer (A-3) had a weight average molecular weight (Mw) in terms of polystyrene of 11,500. Moreover, the solid content concentration of the polymer solution obtained here was 30.9 mass%.
[Synthesis Example 4] (Synthesis of Polymer (A-4))
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate. Subsequently, 10 parts by weight of methacrylic acid, 40 parts by weight of 4-hydroxyphenyl methacrylate, 40 parts by weight of 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl methacrylate, 10 parts by weight of hydroxyethyl methacrylate Was added, and the mixture was purged with nitrogen. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-4). The polystyrene equivalent weight average molecular weight (Mw) of the polymer (A-4) was 9,000. Moreover, the solid content concentration of the polymer solution obtained here was 33.0 mass%.
[Synthesis Example 5] (Synthesis of polymer (CA-1))
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 45 parts by mass of 4-hydroxyphenyl methacrylate, 35 parts by mass of benzyl methacrylate, and 20 parts by mass of methacrylic acid were charged and purged with nitrogen, and then gently agitated. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (CA-1). The weight average molecular weight (Mw) in terms of polystyrene of the polymer (CA-1) was 8,500. Moreover, the solid content concentration of the polymer solution obtained here was 31.6 mass%.
[Synthesis Example 6] (Synthesis of polymer (CA-2))
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 50 parts by mass of glycidyl methacrylate, 10 parts by mass of styrene, and 40 parts by mass of benzyl methacrylate were charged and purged with nitrogen, and then gently agitated. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (CA-2). The polymer (CA-2) had a weight average molecular weight (Mw) in terms of polystyrene of 10,000. Moreover, the solid content concentration of the polymer solution obtained here was 31.0 mass%.
[Synthesis Example 7] (Synthesis of polymer (CA-3))
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 20 parts by mass of methacrylic acid, 20 parts by mass of p-hydroxystyrene, 10 parts by mass of styrene, 20 parts by mass of 4-hydroxyphenyl methacrylate, and 30 parts by mass of butyl methacrylate were charged and purged with nitrogen. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (CA-3). The polymer (CA-3) had a polystyrene equivalent weight average molecular weight (Mw) of 11,000. Moreover, the solid content concentration of the polymer solution obtained here was 30.0 mass%.
[Synthesis Example 8] (Synthesis of polymer (CA-4))
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 20 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate, 30 parts by mass of 3-methacryloyloxymethyl-3-ethyloxetane, 10 parts by mass of styrene, and 40 parts by mass of benzyl methacrylate were substituted with nitrogen, and then gently stirred. I started. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (CA-4). The polymer (CA-4) had a weight average molecular weight (Mw) in terms of polystyrene of 11,500. Moreover, the solid content concentration of the polymer solution obtained here was 30.9 mass%.
[Synthesis Example 9] (Synthesis of Polymer (a-1) of Comparative Example)
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 50 parts by mass of 1-ethoxyethyl methacrylate, 40 parts by mass of glycidyl methacrylate, and 10 parts by mass of hydroxyethyl methacrylate methacrylate were charged and purged with nitrogen. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (a-1). The polystyrene equivalent weight average molecular weight (Mw) of the polymer (a-1) was 8,500. Moreover, the solid content concentration of the polymer solution obtained here was 31.2 mass%.
<Preparation of radiation-sensitive resin composition>
[B] Nonionic photoacid generator, [C] compound, [D] compound, and [E] compound used for the preparation of the radiation sensitive resin composition are shown below.
[[B] Nonionic photoacid generator]
B-1: 5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (IRGACURE PAG 103, manufactured by BASF)
B-2: (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (IRGACURE PAG 121, manufactured by BASF)
B-3: (5-octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile (CGI-725, manufactured by BASF)
B-4: An oxime sulfonate compound represented by the following formula ("IRGACURE PAG 203" manufactured by BASF)

B-5: Compound having naphthalimide structure represented by the following formula

B-6: Compound having naphthalimide structure represented by the following formula

[[C] acid crosslinking agent]
C-1: N, N, N, N-tetra (methoxymethyl) glycoluril C-2: N, N, N, N, N, N-hexa (methoxymethyl) melamine C-3: N, N-di (Methoxymethyl) urea,
C-4: N, N-di (methoxymethyl) -4,5-di (methoxymethyl) ethyleneurea [[D] antioxidant]
D-1: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (ADK STAB AO-60, manufactured by ADEKA)
D-2: Tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate (ADK STAB AO-20, manufactured by ADEKA)
[[E] basic compound]
E-1: Triphenylsulfonium salicylate E-2: 2-phenylbenzimidazole [Example 1]
[A] In a polymer solution containing (A-1) as a polymer component (amount corresponding to 100 parts by mass (solid content) of (A-1)), [B] as a nonionic photoacid generator (B-1) 3.0 parts by mass, (C-1) 15 parts by mass as a photocrosslinking agent, and (D-1) 1 part by mass as an antioxidant (D-1), [E] base A radiation-sensitive resin composition was prepared by mixing 0.1 part by mass of (E-1) triphenylsulfonium salicylate as a functional compound and filtering with a membrane filter having a pore size of 0.2 μm. Table 1 shows.
[Examples 2-5, 9 and Comparative Examples 1-2]
Except having used each component of the kind and compounding quantity shown in following Table 1, it operated similarly to Example 1 and prepared each radiation sensitive resin composition. In addition, "-" in Table 1 indicates that the corresponding component was not blended. Table 1 shows.

  Comparative Example 1 uses the polymer (a-1) of Comparative Example shown in [Synthesis Example 9] as the [A] polymer component, and [B] (B-1 as a nonionic photoacid generator). ) Was used in the same manner as in Example 1, except that 3 parts by mass of (E) and 0.1 part by mass of (E-2) as a basic compound were prepared. This radiation sensitive resin composition becomes a negative type radiation sensitive resin composition.

Comparative Example 2 uses the polymer (a-1) as the [A] polymer component, [B] 3 parts by mass of (B-1) as a nonionic photoacid generator, and [C] light. 10 parts by mass of (C-2) as a crosslinking agent, 1 part by mass of (D-1) as an antioxidant [D], and 0.1 part by mass of (E-2) as a basic compound [E] In the same manner as in Comparative Example 1, a negative radiation sensitive resin composition was prepared. Table 1 shows.
[Example 6]
A polymer solution containing (CA-1) (an amount corresponding to 50 parts by mass (solid content) of (CA-1)) and a polymer solution containing (CA-2) (50 parts by mass of (CA-2) ( (B) 3 parts by weight as [B] nonionic photoacid generator, and [C] as compound [C] (C-1) 20 parts by mass, [D] 1 part by mass of (D-1) as an antioxidant, and [E] 0.1 part by mass of triphenylsulfonium salicylate as a basic compound were mixed. A radiation sensitive resin composition was prepared by filtering through a membrane filter having a pore size of 0.2 μm. Table 1 shows.
[Examples 7 to 8, 10]
Except having used each component of the kind and compounding quantity which are shown in following Table 1, it operated similarly to Example 5 and prepared each radiation sensitive resin composition. Table 1 shows.

<Evaluation>
The following evaluation was implemented using each prepared radiation sensitive resin composition. The results are shown in Table 2.

[Resolution (μm)]
Each radiation-sensitive resin composition solution was applied onto an alkali-free glass substrate with a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. Subsequently, the exposure amount is set to 200 J / m ^{2 to} 1,000 J / M using a high-pressure mercury lamp through a photomask having a plurality of circular residual patterns with different sizes in the diameter range of ⁸ μm to ²⁰ μm. Irradiation was performed with variable amount in the range of m ² . Thereafter, shower development was performed by discharging a 0.5% by mass tetramethylammonium hydroxide aqueous solution as a developing solution at a developing pressure of 1 kgf / cm ² and a nozzle diameter of 1 mm, followed by washing with pure water for 1 minute. Further, a patterned coating film was formed by post-baking in an oven at 230 ° C. for 30 minutes. At this time, the minimum pattern size to be formed was defined as the resolution (μm). If a pattern having a size of 10 μm or less is formed in a photomask of 12 μm or less, it can be determined that the resolution is good.
[Sensitivity (J / m ² )]
Hexamethyldisilazane (HMDS) was applied to a glass substrate of 550 mm × 650 mm and heated at 60 ° C. for 1 minute. Each composition was applied to the chromium-deposited glass substrate after the HMDS treatment using a slit die coater (TR6321005-CL, manufactured by Tokyo Ohka Kogyo Co., Ltd.), the ultimate pressure was set to 100 Pa, and the solvent was removed under vacuum. Thereafter, it was further pre-baked at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. Subsequently, using an exposure machine (MPA-600FA, ghi line mixing, manufactured by Canon), the exposure amount was changed to the coating film through a mask having a 60 μm line and space (10 to 1) pattern. Irradiated. Then, it developed by the piling method for 80 seconds at 25 degreeC with 0.5 mass% tetramethylammonium hydroxide aqueous solution. Next, washing with running ultrapure water for 1 minute was performed, followed by drying to form a pattern on the chromium-deposited glass substrate after the HMDS treatment. At this time, the amount of exposure necessary to completely dissolve the 6 μm space pattern was examined. When the exposure value is 500 (J / m ² ) or less, it can be determined that the sensitivity is good.
[Evaluation of light resistance]
Each radiation sensitive resin composition solution was applied onto a silicon substrate using a spinner and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. This silicon substrate was heated in a clean oven at 220 ° C. for 1 hour to obtain a cured film. Each obtained cured film was irradiated with 800,000 J / m ² at an illuminance of 130 mW with a UV irradiation apparatus (“UVX-02516S1JS01” manufactured by USHIO Co., Ltd.). It can be said that the light resistance of the cured film is good when the amount of film thickness reduction after irradiation is 3% or less compared to the film thickness before irradiation.

In the evaluation of light resistance, patterning of the cured film to be formed is unnecessary, and therefore the development process was omitted, and only the coating film forming process, the light resistance test, and the heating process were performed for evaluation.
[Evaluation of transmittance]
A coating film was formed on a silicon substrate in the same manner as the light resistance evaluation. This silicon substrate was heated in a clean oven at 220 ° C. for 1 hour to form a cured film. About each obtained cured film, the transmittance | permeability in wavelength 400nm was measured and evaluated using the spectrophotometer ("150-20 type double beam" by Hitachi, Ltd.). At this time, if it is less than 90%, it can be said that the transparency is poor.
[Voltage holding ratio (%)]
After spin-coating each radiation-sensitive resin composition on a soda glass substrate on which a SiO2 film for preventing elution of sodium ions is formed on the surface, and an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape The film was pre-baked for 10 minutes in a clean oven at 90 ° C. to form a coating film having a thickness of 2.0 μm. Next, the coating film was exposed at an exposure amount of 500 J / m ² without using a photomask. Thereafter, the substrate is immersed in a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, air-dried, and further post-treated at 230 ° C. for 30 minutes. Baking was performed and the coating film was cured to form a permanent cured film. Next, the substrate on which this pixel is formed and the substrate on which the ITO electrode is simply deposited in a predetermined shape are bonded together with a sealant mixed with 0.8 mm glass beads, and then Merck liquid crystal (MLC6608) is injected. A liquid crystal cell was produced. Next, the liquid crystal cell was placed in a constant temperature bath at 60 ° C., and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage holding ratio measuring system (VHR-1A type, Toyo Corporation). The applied voltage at this time is a square wave of 5.5 V, and the measurement frequency is 60 Hz. Here, the voltage holding ratio is a value of (liquid crystal cell potential difference after 16.7 milliseconds / voltage applied at 0 milliseconds). If the voltage holding ratio of the liquid crystal cell is 90% or less, it means that the liquid crystal cell cannot hold the applied voltage at a predetermined level for a time of 16.7 milliseconds, and the liquid crystal cannot be sufficiently aligned. There is a high risk of causing “burn-in”.
[Evaluation observation of thermal stability of pattern shape]
The substrate on which the pattern formed by the sensitivity evaluation was formed was additionally heated in a clean oven at 230 ° C. for 1 hour, and the shape of the formed pattern was observed with an SEM (scanning electron microscope).
When the pattern shape melt-flowed from the rectangular shape to the dome shape by additional heating, the thermal stability of the pattern shape was judged to be poor. When it was good, it was marked with “◯”, and when it was bad, it was marked with “x”.
[Evaluation of ITO adhesion of pattern]
A cured film was formed by the same operation as described above except that an ITO-attached substrate was used instead of the silicon substrate in the light resistance evaluation, and a pressure cooker test (120 ° C., humidity 100%, 4 hours) was performed. Thereafter, “JIS K-5400-1990, 8.5.3 Adhesive cross-cut tape method” was performed to determine the number of cross-cuts remaining in 100 cross-cuts, and the ITO adhesion of the cured film was evaluated. When the number of grids remaining in 100 grids is 80 or less, it can be determined that the ITO adhesion is poor. The number of remaining grids is shown in Table 2.

As is clear from the results in Table 2, the negative radiation-sensitive resin composition can be patterned with resolution and sensitivity, and when evaluated as a cured film, transmittance, light resistance, voltage holding ratio, pattern It was found to have thermal stability of the shape and ITO adhesion.

Claims (7)

[A] Crosslinkable group which is at least one selected from the group consisting of structural unit (I) containing phenolic hydroxyl group and (meth) acryloyl group, vinyl group, oxiranyl group and oxetanyl group in the same or different polymers A polymer component comprising a structural unit (II) containing a structural unit (III) containing a carboxyl group,
[B] A nonionic photoacid generator which is at least one selected from a compound having an oxime sulfonate structure represented by the following formula (1) and a compound having a naphthalimide structure represented by the following formula (2); A negative radiation-sensitive resin composition containing an acid crosslinking agent.

(In Formula (1), R1 is an alkyl group, an alicyclic hydrocarbon group, an aryl group, or a part or all of the hydrogen atoms of these alkyl groups, alicyclic hydrocarbon groups, and aryl groups are substituents. A group substituted with


(In Formula (2), R18 and R21 to R23 are hydrogen atoms. One of R19 and R20 is a linear or branched alkoxy group having 4 to 18 carbon atoms, adjacent to the oxygen atom of this alkoxy group. A group in which the methylene group at any position is substituted with a —C (═O) — group, and the above alkoxy group is closer to the naphthalene ring from the —O—C (═O) — bond or —OC (═O) —NH -A group interrupted by a bond, a linear or branched alkylthio group having 4 to 18 carbon atoms, or a methylene group at any position not adjacent to the sulfur atom of the alkylthio group is substituted with a -C (= O)-group. A group interrupted by an —O—C (═O) — bond or —OC (═O) —NH— bond from the side closer to the naphthalene ring, or the following formula (3): A group of R19 and R20 Some or all of the hydrogen atoms of the ruxoxy group and the alkylthio group may be substituted with an alicyclic hydrocarbon group, a heterocyclic group or a halogen atom, and the other of R19 and R20 is a hydrogen atom. An unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, an unsubstituted linear or branched alkyl group having 1 to 18 carbon atoms, and an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms An unsubstituted aryl group having 6 to 20 carbon atoms, an unsubstituted arylalkyl group having 7 to 20 carbon atoms, an unsubstituted alkylaryl group having 7 to 20 carbon atoms, a 10-camphoryl group, or the following formula (4 ).

(In Formula (3), R25 is a C1-C12 divalent hydrocarbon group. R26 is a C1-C4 alkanediyl group. R27 is a hydrogen atom, C1-C1. 4 a linear or branched alkyl group, a monovalent alicyclic hydrocarbon group or a monovalent heterocyclic group having 3 to 10 carbon atoms, and Y1 is an oxygen atom or a sulfur atom. Is a single bond or an alkanediyl group having 1 to 4 carbon atoms, and g is an integer of 0 to 5.)

(In Formula (4), R28 is an alkanediyl group having 2 to 6 carbon atoms and an arylene group having 6 to 20 carbon atoms. R29 is a single bond, an alkanediyl group having 2 to 6 carbon atoms, and 6 carbon atoms. R30 is a linear or branched alkyl group having 1 to 18 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aryl having 6 to 20 carbon atoms. Group is an arylalkyl group having 7 to 20 carbon atoms, Y3 is a single bond or an alkanediyl group having 1 to 4 carbon atoms, and one of h and i is 1 and the other is 0 or 1. .) The negative radiation-sensitive resin composition according to claim 1, wherein the [C] acid crosslinking agent has a structure represented by the following formula (5).

(In Formula (5), R2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. M is an integer of 1 to 3.) The negative radiation-sensitive radiation according to any one of claims 1 to 2 , wherein the structural unit (I) containing the phenolic hydroxyl group of the [A] polymer is a structural unit represented by the following formula (6). Resin composition.

(In the formula (6), X represents a direct bond, —COO— or —CONH—, R 3 represents a direct bond, a methylene group, or an alkylene group having 2 to 6 carbon atoms, and R 4 represents a hydrogen atom or 1 carbon atom. An alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen, n is an integer from 1 to 4.) [D] The negative radiation sensitive resin composition according to any one of claims 1 to 3 , further comprising an antioxidant. The cured film formed from the negative radiation sensitive resin composition of any one of Claims 1-4 . (1) The process of forming a coating film on a board | substrate using the negative radiation sensitive resin composition of any one of Claims 1-5 ,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) The process of developing the coating film irradiated with the said radiation, (4) The formation method of the cured film which has the process of heating the said developed coating film. A display element provided with the cured film of Claim 6 .