JP5814143B2 - Photosensitive resin composition and method for producing pattern using the same - Google Patents

Description

  The present invention relates to a positive photosensitive resin composition, a method for producing a pattern, an organic EL display device, a method for producing a liquid crystal display device, and a cured film. More specifically, the present invention relates to a positive photosensitive resin composition suitable for forming resist etching of electronic parts such as liquid crystal display devices and organic EL display devices, and a pattern manufacturing method using the same.

  An organic EL display device, a liquid crystal display device, and the like are provided with a metal wiring pattern such as a patterned ITO film. For pattern formation of this ITO film and the like, a method is widely known in which a photosensitive resin composition is applied on the ITO film, the solvent is removed, exposed and developed, and the ITO film is etched using the formed pattern as a mask and processed. It has been.

  In recent years, high resolution of ITO processing has been demanded in order to make organic EL display devices and liquid crystal display devices have high-definition display characteristics. In order to finely process ITO with high definition, high resolution of a photosensitive resin composition that functions as a mask during etching is required.

  As a photosensitive resin composition capable of obtaining a high-definition and fine pattern shape, for example, Patent Document 1 discloses a co-polymer consisting of a repeating unit of a hydroxystyrene monomer and a repeating unit of a hydroxystyrene monomer in which a hydroxyl group is protected. A radiation sensitive resin composition containing a coalescence is disclosed.

  With the composition described in Patent Document 1, a high-definition and fine pattern can be formed. However, to produce these copolymers, it is necessary to perform costly living polymerization. If the polymerization method of these copolymers is changed to radical polymerization with a low cost, the molecular weight distribution of the copolymers becomes wide and the low molecular weight components increase. Thereby, the softening point of the film is lowered, and there is a problem that a rectangular pattern shape (rectangularity) may not be obtained after development. Moreover, when this inventor examined the composition of the cited reference 1, it turned out that a sensitivity, line | wire width sensitivity stability (PED: Post Exposure Time Delay), adhesiveness, and thinning are not satisfactory. It was.

JP 9-325473 A

  The present invention has been made to solve the above-described problems, and is a photosensitive resin composition excellent in rectangularity, sensitivity, PED, resolution, and remaining film properties, a pattern manufacturing method, an organic EL display device, It is an object to provide a method for manufacturing a liquid crystal display device and a cured film.

As a result of intensive studies by the inventors of the present invention based on the above-mentioned problems, the combined use of two specific polymers and parahydroxystyrene resin increases the alkali dissolution rate, thereby increasing the sensitivity. The diffusion of the acid generated from the generating agent is promoted to improve the PED characteristics, and the binder Tg is further increased to improve the heat resistance of the pixel and to maintain the rectangularity after the post-baking. It was found that the above problems can be solved.
The means for solving the problem is the means [1] below, preferably the means [2] to [13] below.
[1] (A1) A polymer containing a repeating unit (a1) represented by the following general formula (I) and a repeating unit (a2) represented by the following general formula (II):
(A2) a polymer containing a repeating unit (a3) represented by the following general formula (III) and a repeating unit (a2) represented by the following general formula (II):
(B) a parahydroxystyrene resin having a weight average molecular weight of 2000 to 15000 and a polydispersity of 1.5 to 5.0,
(C) a photoacid generator,
A positive photosensitive resin composition comprising (D) a basic compound and (E) a solvent.
(In general formula (I), R ² represents a hydrogen atom or a methyl group, R ³ represents a hydrogen atom, a chain alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or 6 carbon atoms. Represents an aryl group having 10 to 10 carbon atoms or an aralkyl group having 7 to 11 carbon atoms, and R ⁴ and R ⁵ are each independently a chain alkyl group having 1 to 10 carbon atoms, a halogenated chain alkyl group having 1 to 10 carbon atoms, A cyclic alkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 11 carbon atoms;
In general formula (II), R ¹ represents a hydrogen atom or a methyl group;
In general formula (III), Ra ^{1 to} Ra ⁶ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group. Ra ² and Ra ³ , Ra ⁴ and Ra ⁵ may be bonded to each other to form a ring. Ra ⁷ represents a hydrogen atom or a methyl group, Ra ⁸ represents a halogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms, and n1 represents an integer of 0 to 4. )
[2] The component (A1) is a polymer (A1 ′) having a repeating unit represented by the following general formula (I ′) and a repeating unit represented by the following general formula (II ′):
The component (A2) is a polymer (A2 ′) having a repeating unit represented by the following general formula (III ′) and a repeating unit represented by the following general formula (II ′):
The positive photosensitive resin composition according to [1], comprising at least one of the polymer (A1 ′) and the polymer (A2 ′).
(In the general formula (I ′), R ⁶ represents an alkyl group having 1 to ⁶ carbon atoms. In the general formula (III ′), Ra ¹¹ and Ra ¹² are each independently a hydrogen atom or a carbon atom having 1 to 6 carbon atoms. Represents an alkyl group or a phenyl group, and Ra ¹¹ and Ra ¹² may be bonded to each other to form a 5- to 7-membered ring.)
[3] The positive photosensitive resin composition according to [1] or [2], wherein the (C) photoacid generator includes an oxime sulfonate structure represented by the following general formula (b1).
(In the general formula (b1), R ¹ represents an alkyl group, a cycloalkyl group, a heteroaryl group, or an aryl group.)
[4] The basic compound (D) is a compound represented by the following general formula (Qa), a compound represented by the following general formula (Qb), and the following general formula (Qc). The positive photosensitive resin composition in any one of [1]-[3] containing at least 1 sort (s) of the compound represented.
(In General Formula (a), R ² represents an alkyl group which may have a substituent having 1 to 6 carbon atoms or a cycloalkyl group which may have a substituent having 3 to 10 carbon atoms. X represents an oxygen atom or a sulfur atom, Y ¹ represents an oxygen atom or a —NH— group, and p1 represents an integer of 1 to 3.)
(In the general formula (Qb), R ⁸ , R ⁹ and R ¹⁰ each independently have a hydrogen atom, an alkyl group which may have a substituent of 1 to 6 carbon atoms, or a substituent. Represents an aryl group which may be substituted, or a cycloalkyl group which may have a substituent having 3 to 10 carbon atoms.
[5] The weight average molecular weight of at least one of the component (A1) and the component (A2) is 2000 to 15000, and the polydispersity is 1.5 to 5.0. Any positive photosensitive resin composition.
[6] The positive photosensitive resin composition according to any one of [1] to [5], wherein the content of the component (A2) is 30 to 97% by weight with respect to the entire photosensitive resin composition.
[7] The positive photosensitive resin composition according to any one of [1] to [6], wherein the weight ratio (A1: A2) between the component (A1) and the component (A2) is 50:50 to 5:95. object.
[8] The positive photosensitive resin composition according to any one of [1] to [7], wherein 95% by weight or more of the polymer component contained in the photosensitive resin composition is composed of repeating units derived from hydroxystyrene.
[9] (1) A step of applying the positive photosensitive resin composition according to any one of [1] to [9] on a substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) a step of exposing with actinic radiation,
(4) a step of developing with an aqueous developer,
(5) etching the substrate using the formed resist pattern as a mask, and
(6) A method for producing a pattern comprising the step of stripping the resist pattern.
[10] The method for producing a pattern according to [9], including a step of post-baking the resist pattern at 100 to 160 ° C. after the developing step and before the etching step.
[11] The substrate is an ITO substrate, IGZO substrate, molybdenum substrate, Ti substrate, Al substrate, Cu substrate, tungsten substrate, silicon oxide substrate, silicon nitride substrate, or silicon substrate [9] or The method for producing a pattern according to [10].
[12] A method for producing an organic EL display device or a liquid crystal display device, comprising the method for producing a pattern according to any one of [9] to [11].
[13] A cured film obtained by curing the positive photosensitive resin composition according to any one of [1] to [8].

  According to the present invention, a positive photosensitive resin composition excellent in rectangularity, sensitivity, PED, resolution, and residual film property, a pattern manufacturing method, an organic EL display device, a liquid crystal display device manufacturing method, and a cured film are provided. Can be provided.

1 shows a conceptual diagram of a configuration of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided. 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device. The schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. Moreover, the organic EL display device in the present invention refers to an organic electroluminescence display device (organic electroluminescence element).
The polydispersity in the present invention refers to the value of Mw / Mn.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention comprises (A1) a polymer containing a repeating unit (a1) represented by the following general formula (I) and a repeating unit (a2) represented by the following general formula (II): (A2) a polymer containing a repeating unit (a3) represented by the following general formula (III) and a repeating unit (a2) represented by the following general formula (II), (B) a weight average molecular weight of 2000 to 15000 A polyhydroxystyrene resin having a polydispersity of 1.5 to 5.0, (C) a photoacid generator, (D) a base compound, and (E) a solvent.
(In general formula (I), R ² represents a hydrogen atom or a methyl group, R ³ represents a hydrogen atom, a chain alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or 6 carbon atoms. Represents an aryl group having 10 to 10 carbon atoms or an aralkyl group having 7 to 11 carbon atoms, and R ⁴ and R ⁵ are each independently a chain alkyl group having 1 to 10 carbon atoms, a halogenated chain alkyl group having 1 to 10 carbon atoms, A cyclic alkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 11 carbon atoms is represented.)

(In general formula (II), R ¹ represents a hydrogen atom or a methyl group.)

(In General Formula (III), Ra ^{1 to} Ra ⁶ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group. Ra ² and Ra ³ , Ra ⁴ and Ra ⁵ may be bonded to each other to form a ring, Ra ⁷ represents a hydrogen atom or a methyl group, and Ra ⁸ represents a halogen atom or a hydroxyl group. Or represents a C1-C3 alkyl group, and n1 represents the integer of 0-4.)

  Hereinafter, each component of the photosensitive resin composition of this invention is demonstrated.

<(A) component>
The photosensitive resin composition of the present invention (hereinafter also referred to as the photosensitive composition of the present invention or the composition of the present invention) has (A1) as a component (A1) a repeating unit represented by the following general formula (I) A polymer containing (a1) and a repeating unit (a2) represented by the following general formula (II), (A2) a repeating unit (a3) represented by the following general formula (III) and the following general formula (II) And a polymer containing a repeating unit (a2) represented by
The component (A) may contain other repeating units (a4) in addition to the repeating units (a1) to (a3).

  Although detailed mechanism is unknown, in this invention, it is excellent in rectangularity, a sensitivity, and PED by including the polymer of A1 component and A2 component as (A) component.

  The component (A) is preferably insoluble or hardly soluble in alkali, and becomes alkali-soluble when the protected hydroxy group of the monomer unit (a1) is decomposed by the action of an acid. It is preferable that As a resin whose solubility in an alkaline developer is increased by the action of such an acid, it has a repeating unit corresponding to hydroxystyrene having the monomer unit (a1), and is decomposed by the action of an acid to increase the solubility in alkali. Resin is used. Here, in the present invention, “alkali-soluble” means a coating film (thickness) of the compound (resin) formed by applying a solution of the compound (resin) on a substrate and heating at 90 ° C. for 2 minutes. 3 μm) at 23 ° C. in a 2.38% tetramethylammonium hydroxide aqueous solution is 0.01 μm / second or more. “Alkali insoluble” means that the solution of the compound (resin) is a substrate. The dissolution rate of the coating film (thickness: 3 μm) of the compound (resin) formed by coating on the substrate and heating at 90 ° C. for 2 minutes in a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C. It means less than 0.01 μm / second.

<< (A1) component >>
The component (A1) in the photosensitive resin composition of the present invention contains a repeating unit (a1) represented by the following general formula (I) and a repeating unit (a2) represented by the following general formula (II). It is a polymer.

(In general formula (I), R ² represents a hydrogen atom or a methyl group, R ³ represents a hydrogen atom, a chain alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or 6 carbon atoms. Represents an aryl group having 10 to 10 carbon atoms or an aralkyl group having 7 to 11 carbon atoms, and R ⁴ and R ⁵ are each independently a chain alkyl group having 1 to 10 carbon atoms, a halogenated chain alkyl group having 1 to 10 carbon atoms, Represents a cyclic alkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 11 carbon atoms.) Any two of R ³ , R ⁴ , and R ⁵ are bonded to each other. It does not form a ring.

R ² is a hydrogen atom or a methyl group, preferably a hydrogen atom.

R ³ represents a hydrogen atom, a chain alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 11 carbon atoms. Examples of R ³ are hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, s-butyl group, t- Butyl group, Neopentyl group, Cyclopentyl group, Cyclohexyl group, Cycloheptyl group, Cyclooctyl group, Cyclononyl group, Cyclodecyl group, Phenyl group, Naphtyl group, Benzyl group, Ethylphenyl group, Propylphenyl group, Isopropylphenyl group, Butylphenyl Group, t-butylphenyl group, s-butylphenyl group and the like, and a hydrogen atom and a methyl group are preferable. These may further have a substituent.

Preferred substituents that R ³ in the general formula (I) may have include an alkyl group, an alkoxy group, an aryl group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acyloxy group, an acylamino group, a sulfonylamino group, an alkylthio group. Groups, arylthio groups, aralkylthio groups, thiophenecarbonyloxy groups, thiophenemethylcarbonyloxy groups, and heterocyclic residues such as pyrrolidone residues. These substituents preferably have 12 or less carbon atoms. Further, these groups may be further substituted with these groups.

Specific examples of preferable substituents that the alkyl group represented by R ³ in the general formula (I) may have include, for example, pt-butylbenzylcarbonyloxy group, p-methoxybenzylcarbonyloxy group, 2-thiophenecarbonyloxy group. Group, 3-thiophenemethylcarbonyloxy group, N-pyrrolidonyl group, phenyl group, cyclohexyl group, phenylthio group, cyclohexylthio group, 4-t-butylcyclohexylcarbonyloxy group, 4-butylcyclohexylcarbonyloxy group and the like.

R ⁴ and R ⁵ are each independently a chain alkyl group having 1 to 10 carbon atoms, a halogenated chain alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, and an aryl having 6 to 10 carbon atoms. Represents a group or an aralkyl group having 7 to 11 carbon atoms. Examples of R ⁴ and R ⁵ are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, s-butyl, t- Butyl group, neopentyl group, s-pentyl group, t-pentyl group, s-hexyl group, t-hexyl group, s-heptyl group, t-heptyl group, s-octyl group, t-octyl group, s-nonyl group T-nonyl group, s-decyl group, t-decyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, phenyl group, naphthyl group, benzyl group, ethylphenyl group, pro Pullphenyl, isopropylphenyl, butylphenyl, t-butylphenyl, s-butylphenyl, chloromethyl, chloroe Group, chloropropyl group, chlorobutyl group, chloropentyl group, chlorohexyl group, chlorohepta group, chloroocta group, chlorononyl group, chlorodecyl group, bromomethyl group, bromoethyl group, bromopropyl group, bromobutyl group, bromopentyl group, bromohexyl group , A bromohepta group, a bromoocta group, a bromononyl group, a bromodecyl group, and the like, and a methyl group, an ethyl group, a propyl group, a t-butyl group, and a cyclohexyl group are preferable. These may further have a substituent.

Preferable substituents that R ⁴ and R ⁵ may have are the same as the preferable substituents that R ³ of the general formula (I) may have.

  The general formula (I) is preferably represented by the following general formula (I ′).

(In General Formula (I ′), R ⁶ represents an alkyl group having 1 to ⁶ carbon atoms.)

R ⁶ is an alkyl group having 1 to 6 carbon atoms, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a pentyl group, and a cyclopentyl group. , A straight-chain, branched or cyclic group having 1 to 6 carbon atoms such as a hexyl group and a cyclohexyl group, and a methyl group, an ethyl group, a propyl group, a t-butyl group and a cyclohexyl group are preferable.

R ⁶ may further have a substituent, and preferred substituents that R ⁶ may have are the same as the preferred substituents that R ³ of the general formula (I) may have.

In the present invention, it is particularly preferable that R ³ is a hydrogen atom, R ⁴ is a methyl group, and R ⁵ is an unsubstituted alkyl group or an alkyl group substituted with an alkyl group or an aryl group. The number of carbon atoms of R ^5, including a substituent is preferably from 1 to 20, 1 to 12 is more preferable.

(In general formula (II), R ¹ represents a hydrogen atom or a methyl group.)

R ¹ is a hydrogen atom or a methyl group, preferably a hydrogen atom.

  The skeleton of the repeating unit (a2) represented by the general formula (II) may be partially hydrogenated.

  Here, the skeleton of the monomer unit of hydroxystyrene may be any of o-, m-, or p-hydroxystyrene in the monomer unit (a1) and the monomer unit (a2). From the viewpoint of the pattern shape, a p-hydroxystyrene skeleton is preferable.

  The general formula (II) is preferably represented by the following general formula (II ′).

  The component A1 is preferably a polymer (A1 ′) containing a repeating unit represented by the above general formula (I ′) and a repeating unit represented by the following general formula (II ′).

[Other monomer (a4)]
The component (A) may include structural units derived from other monomers in addition to the repeating units (a1) and (a2) constituting the component A1. Other monomers include hydrogenated hydroxystyrene; halogen, alkoxy or alkyl-substituted hydroxystyrene; styrene; halogen, alkoxy, acyloxy or alkyl-substituted styrene; maleic anhydride; acrylic acid derivative; methacrylic acid derivative; N-substituted maleimide and the like. It can be mentioned, but is not limited to these.

  The content of the other monomer (a4) is preferably 20% by weight or less, and more preferably 5% by weight or less based on the component A1.

The ratio of the sum of the repeating unit (a1) and the repeating unit (a2) to the structural unit of the other monomer is a molar ratio of [monomer unit (a1) + monomer unit (a2)] / [other monomer components] ] = 100/0 to 80/20, preferably 100/0 to 95/5, more preferably 100/0 to 97/3.
In particular, in the present invention, among the repeating units constituting the component (A1), it is preferable that the amount other than the repeating unit derived from the hydroxystyrene derivative is 3 mol% or less, and more preferably substantially not contained. “Substantially free” means, for example, that the effect of the present invention is not affected.

  The following are mentioned as a specific example of resin containing the repeating structural unit shown by the above-mentioned general formula (I) and general formula (II).

  In the above specific examples, Me represents a methyl group, Et represents an ethyl group, n-Bu represents an n-butyl group, iso-Bu represents an isobutyl group, and t-Bu represents a t-butyl group. Among the specific examples, (IV-2) to (IV-14) are preferable, (IV-2), (IV-3), (IV-4), (IV-8), and (IV-9). Is more preferable.

  The ratio of the repeating unit (a1) represented by the general formula (I) and the repeating unit (a2) represented by the general formula (II) is preferably 1/99 to 60/40, more preferably It is 5 / 95-50 / 50, More preferably, it is 10 / 90-40 / 60.

  The protection rate of A1 component becomes like this. Preferably it is 1-60%, More preferably, it is 5-50%, More preferably, it is 10-40%. The protection rate refers to the molar ratio of the derivative unit in which the total of hydroxystyrene and its derivative units in the polymer is 100%, and the hydrogen atom of the hydroxyl group is substituted with another substituent.

  The weight average molecular weight (Mw) of the A1 component is preferably in the range of 2000 to 15000, more preferably 5000 to 12000, and still more preferably 7500 to 12000. By setting it to 2000 or more, an effect that the formed pixel can maintain rectangularity after heating by post-baking is obtained, and by setting it to 15000 or less, an effect that sensitivity and PED characteristics are improved is obtained. Here, the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.

  The polydispersity of the A1 component (weight average molecular weight (Mw) / number average molecular weight (Mn)) is preferably 1.5 to 5.0, more preferably 1.7 to 3.0, and 1.9 to 2 .5 is more preferred. When the polydispersity is less than 1.5 or exceeds 5.0, the line width sensitivity stability (PED characteristics) and sensitivity are lowered, and the rectangularity is lowered, which is not preferable.

<< A2 component >>
The component (A2) in the photosensitive resin composition of the present invention contains a repeating unit (a3) represented by the following general formula (III) and a repeating unit (a2) represented by the above general formula (II). It is a polymer.
(In General Formula (III), Ra ^{1 to} Ra ⁶ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group. Ra ² and Ra ³ , Ra ⁴ and Ra ⁵ may be bonded to each other to form a ring, Ra ⁷ represents a hydrogen atom or a methyl group, and Ra ⁸ represents a halogen atom or a hydroxyl group. Or represents a C1-C3 alkyl group, and n1 represents the integer of 0-4.)

The alkyl group in Ra ^{1 to} Ra ⁶ may have a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, which may have a substituent, or a substituent. A phenyl group can be mentioned, A C1-C12 linear, C3-C12 branched, or C5-C10 cyclic alkyl group is preferable. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, Octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, tert-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, A cyclopentyl group, 2-norbornyl group, a phenyl group, and a naphthyl group are mentioned.
Ra ^{1 to} Ra ⁶ are each preferably a hydrogen atom, a linear chain having 1 to 12 carbon atoms, a branched chain having 3 to 12 carbon atoms, or a cyclic alkyl group having 5 to 10 carbon atoms. An embodiment in which a linear alkyl group of 1 to 12 or a phenyl group, Ra ⁴ and Ra ⁵ are bonded to each other to form a six-membered ring is more preferable. A hydrogen atom, a methyl group, a phenyl group, Ra ⁴ and An embodiment in which Ra ⁵ are bonded to each other to form a six-membered ring is more preferable.
Ra ¹ , Ra ² , Ra ³ , Ra ⁶ are preferably hydrogen atoms, and Ra ¹ , Ra ² , Ra ³ , Ra ⁵ are hydrogen atoms, and Ra ⁴ and Ra ⁵ are each More preferably, it is the above group.

The substituent that the alkyl group and aryl group in Ra ^{1 to} Ra ⁶ may have is the same as the preferable substituent that R ³ of the general formula (I) may have.

Ra ⁷ is a hydrogen atom or a methyl group, and preferably a hydrogen atom.
Ra ⁸ is a halogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, preferably a chlorine atom, a bromine atom, a hydroxyl group or a methyl group.
n1 is an integer of 0 to 4, and n1 is preferably 0.

  The general formula (III) is preferably represented by the following general formula (III ′).

(In the general formula (III ′), Ra ¹¹ and Ra ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and Ra ¹¹ and Ra ¹² are bonded to each other to form 5-7. A member ring may be formed.)

Ra ¹¹ and Ra ^{12 each} represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, t -C1-C6 linear, branched or cyclic such as butyl, pentyl, cyclopentyl, hexyl and cyclohexyl groups.

Ra ¹¹ and Ra ¹² may further have a substituent, and preferred substituents that R ⁶ may have are the same as the preferred substituents that R ³ of the general formula (I) may have.

In the present invention, it is particularly preferable that Ra ¹¹ and Ra ¹² are a hydrogen atom, a methyl group, a phenyl group, and a six-membered ring bonded to each other.

  The A2 component is preferably a polymer (A2 ′) containing a repeating unit represented by the general formula (III ′) and a repeating unit represented by the following general formula (II ′). The component A preferably contains at least one of the polymer (A1 ′) and the polymer (A2 ′).

[Other monomer (a4)]
The component (A) may include structural units derived from other monomers in addition to the repeating units (a3) and (a2) constituting the component A2. Other monomers include hydrogenated hydroxystyrene; halogen, alkoxy or alkyl-substituted hydroxystyrene; styrene; halogen, alkoxy, acyloxy or alkyl-substituted styrene; maleic anhydride; acrylic acid derivative; methacrylic acid derivative; N-substituted maleimide and the like. It can be mentioned, but is not limited to these.

  The content of the other monomer (a4) is preferably 20% by weight or less, and more preferably 5% by weight or less based on the component A2.

The ratio of the total of the repeating unit (a3) and the repeating unit (a2) to the structural unit of the other monomer is a molar ratio of [monomer unit (a3) + monomer unit (a2)] / [other monomer components] ] = 100/0 to 80/20, preferably 100/0 to 95/5, more preferably 100/0 to 97/3.
In particular, in the present invention, among the repeating units constituting the component (A2), other than the repeating unit derived from the hydroxystyrene derivative is preferably 3 mol% or less, and more preferably substantially free of it. “Substantially free” means, for example, that the effect of the present invention is not affected.

  The following are mentioned as a specific example of resin containing the repeating structural unit shown by the above-mentioned general formula (III) and general formula (II).

  The ratio of the repeating unit (a3) represented by the general formula (III) and the repeating unit (a2) represented by the general formula (II) is preferably 1/99 to 60/40, more preferably It is 5 / 95-50 / 50, More preferably, it is 10 / 90-40 / 60.

  The protection rate of A2 component becomes like this. Preferably it is 1-60%, More preferably, it is 5-50%, More preferably, it is 10-40%. The protection rate refers to the molar ratio of the derivative unit in which the total of hydroxystyrene and its derivative units in the polymer is 100%, and the hydrogen atom of the hydroxyl group is substituted with another substituent.

  The weight average molecular weight (Mw) of the A2 component is preferably in the range of 2000 to 15000, more preferably 5000 to 12000, and still more preferably 7500 to 12000. By setting it to 2000 or more, an effect that the formed pixel can maintain rectangularity after heating by post-baking is obtained, and by setting it to 15000 or less, an effect that sensitivity and PED characteristics are improved is obtained. Here, the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.

  The polydispersity of the A2 component (weight average molecular weight (Mw) / number average molecular weight (Mn)) is preferably 1.5 to 5.0, more preferably 1.7 to 3.0, and 1.9 to 2 .5 is more preferred. When the polydispersity is less than 1.5 or more than 5.0, the rectangularity and heat resistance are lowered, which is not preferable.

Moreover, you may mix and use 2 or more types of components a1-a3 of the component of the photosensitive composition of this invention. The amount of component (A) used is preferably 40 to 99% by weight, more preferably 60 to 98% by weight, based on the total weight of the photosensitive composition (excluding the solvent).
In the positive photosensitive resin composition of the present invention, 95% by weight or more of the total polymer component contained in the positive photosensitive resin composition of the present invention is preferably a repeating unit derived from a hydroxystyrene derivative, and 97 weights % Or more is more preferably a repeating unit derived from a hydroxystyrene derivative. By adopting such a configuration, it is possible to obtain an effect that a good image pattern with good rectangularity and no residue or film removal development can be obtained. The hydroxystyrene derivative is preferably a p-hydroxystyrene derivative.

The weight ratio of the A1 component to the A2 component (A1 component: A2 component) is preferably 50:50 to 5:95, and more preferably 25:75 to 10:90.
Moreover, 30 to 97 weight% is preferable with respect to the whole photosensitive resin composition, and, as for the content rate of the said A2 component, 50 to 97 weight% is preferable.

In the present invention, the total content of the A1 component and the A2 component is preferably 5 to 50 mol%, more preferably 10 to 40 mol%, based on all repeating units. In the present invention, the total content of the repeating units A1 and A2 is preferably 5 to 95 mol%, more preferably 10 to 85 mol%, based on all repeating units.
The weight average molecular weight (Mw) of the component (A) is preferably in the range of 2,000 to 300,000. If it is less than 2,000, the film loss is large due to the development of the unexposed area. Here, the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.

  The polymer used as the component (A) can be synthesized using either a method using vinyl ether or an acetal exchange method using alcohol and alkyl vinyl ether for acetalization. Moreover, in order to synthesize | combine efficiently and stably, the dehydration azeotropic method as shown in a following example can also be used. However, it is not limited to these synthesis methods.

  The photosensitive resin composition of the present invention is prepared as a solution by dissolving it in a solvent that dissolves each of the above components and then filtering it with a filter having a pore size of about 0.05 μm to 0.2 μm. Examples of the solvent used here include ethylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, 3 -Methyl methoxypropionate, ethyl 3-ethoxypropionate, methyl β-methoxyisobutyrate, ethyl butyrate, propyl butyrate, methyl isobutyl ketone, ethyl acetate, isoamyl acetate, ethyl lactate, toluene, xylene, cyclohexyl acetate, diacetone alcohol, N -Methylpyrrolidone, N, N-dimethylformamide, γ-butyrolactone, N, N-dimethylacetamide, propylene Examples include carbonate and ethylene carbonate. These solvents are used alone or in combination. The selection of the solvent is important because it affects the solubility in the positive photoresist composition of the present invention, the coating property on the substrate, the storage stability, and the like. Further, it is preferable that the amount of water contained in the solvent is small because it affects the performance of the resist.

  Furthermore, in the photosensitive resin composition of the present invention, it is preferable to reduce metal impurities such as metal and impurity components such as chloro ions to 100 ppb or less. The presence of a large amount of these impurities is not preferable because it causes malfunctions, defects, and a decrease in yield in manufacturing a semiconductor device.

  It is preferable that the solid content of the A1 component and the A2 component of the photosensitive resin composition is dissolved in the solvent and dissolved in a solid content concentration of 3 to 40%. More preferably, it is 5-30%, More preferably, it is 7-20%.

<(B) Parahydroxystyrene resin>
The positive photosensitive resin composition of the present invention contains (B) a parahydroxystyrene resin. The parahydroxystyrene resin (also referred to as “component (B)”) used in the present invention has a weight average molecular weight of 2000 to 15000 and a polydispersity of 1.5 to 5.0. By containing the component (B), the alkali solubility is high, the sensitivity is high, the diffusion of the acid generated from the photoacid generator is accelerated, the PED characteristics are improved, and there is no thermal deformation due to post-baking and the rectangularity. There is an advantage that a good pixel can be obtained.

  The weight average molecular weight (Mw) of the said (B) component is 2000-15000, More preferably, it is 5000-12000, More preferably, it is 7500-12000. By setting it to 2000 or more, an effect that the formed pixel can maintain rectangularity after heating by post-baking is obtained, and by setting it to 15000 or less, an effect that sensitivity and PED characteristics are improved is obtained. Here, the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.

  The polydispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the component (B) is 1.5 to 5.0, preferably 1.7 to 3.0, and preferably 1.9 to 2.5 is more preferable. By setting the polydispersity to 1.5 or more, the alkali dissolution rate is high, the sensitivity is high, the diffusion of the acid generated from the photoacid generator is fast, and the PED characteristics are excellent. By setting it as the following, the effect that rectangularity can be maintained after the heating by post-baking is acquired.

  As the parahydroxystyrene resin, a commercially available one and an arbitrarily synthesized one can be used. Specific examples of commercially available parahydroxystyrene resins include Maruza Chemical Co., Ltd., Markalinker MH-2, Markalinker MS-4, Markalinker MS-2, Markalinker MS-1, Japan. Examples include VP-8000 and VP-15000 manufactured by Soda Co., Ltd.

  The content of the component (B) is preferably 5 to 30% by weight and more preferably 10 to 20% by weight with respect to the total solid content of the photosensitive resin composition. By setting it within this range, there is an advantage that PED characteristics, rectangularity, and sensitivity are improved.

<(C) Photoacid generator>
The photosensitive resin composition of the present invention contains (C) a photoacid generator. As the photoacid generator (also referred to as “component (C)”) used in the present invention, a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid is preferable. The chemical structure is not limited. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination. The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, and more preferably a photoacid generator that generates an acid having a pKa of 3 or less. Examples of the photoacid generator include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, quinone diazide compounds, and oxime sulfonate compounds. Among these, from the viewpoint of insulation, it is preferable to use an oxime sulfonate compound or a quinonediazide compound, and an oxime sulfonate compound is more preferable. These photoacid generators can be used singly or in combination of two or more. Specific examples of trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives are described in paragraphs [0083] to [0088] of JP2011-221494A. Can be exemplified.

  In addition to the above, the compounds described in JP-A 2010-282228, paragraphs 0031 to 0052 can also be employed.

Examples of the quinonediazide compound include an o-quinonediazide compound (1,2-quinonediazide compound) and a p-quinonediazide compound (1,4-quinonediazide compound). Among these, from the viewpoints of sensitivity and developability, 1,2-quinonediazide compounds are preferable, and 1,2-naphthoquinonediazide compounds are particularly preferable.
A 1,2-quinonediazide compound can be obtained, for example, by subjecting 1,2-quinonediazidesulfonyl chlorides to a hydroxy compound, an amino compound, or the like in the presence of a dehydrochlorinating agent.
Examples of the 1,2-quinonediazide compound include 1,2-benzoquinonediazidesulfonic acid ester, 1,2-naphthoquinonediazidesulfonic acid ester, 1,2-benzoquinonediazidesulfonic acid amide, and 1,2-naphthoquinonediazidesulfonic acid amide. Etc. Specifically, “Light-Sensitive Systems” by J. Kosar, pp. 339-352 (1965), John Wiley & Sons (New York) and WS De Forest "Photoresist" 50 (1975), McGraw-Hill, Inc, (New York), 1,2-quinonediazide compounds, 1,2-quinonediazide compounds described in JP-A No. 2004-170566, JP-A No. 2002-40653, JP-A No. 2002-351068, JP-A No. 2004-4233, JP-A No. 2004-271975, etc. Can be mentioned. Those described in paragraphs 0066 to 0081 of JP-A-2008-224970 are also preferable.

  Among the compounds having a 1,2-naphthoquinonediazide group, compounds having the following structures can be preferably used because they have particularly high sensitivity.

  Further, the most preferable compound having a 1,2-naphthoquinonediazide group is the following compound. The ratio (molar ratio) of H and 1,2-naphthoquinonediazide group in D is preferably 50:50 to 1:99 from the viewpoint of sensitivity and transparency.

  The oxime sulfonate compound, that is, the compound containing an oxime sulfonate structure is preferably a compound represented by the following general formula (b1).

(In the general formula (b1), R ¹ represents an alkyl group, a cycloalkyl group, a heteroaryl group or an aryl group.)

Any group may be substituted, and the alkyl group in R ¹ may be linear, branched or cyclic. Acceptable substituents are described below.
The alkyl group for R ¹ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group represented by R ¹ is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group or the like It may be substituted with a cyclic group, preferably a bicycloalkyl group or the like.
The aryl group for R ¹ is preferably an aryl group having 6 to 11 carbon atoms, and more preferably a phenyl group or a naphthyl group. The aryl group of R ¹ may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.
As a heteroaryl group of R < ¹ >, the preferable range is the same as the heteroaryl group of R <^22> , R <^25> and R < ²⁸ > in the general formulas (OS-3) to (OS-5) described later.

  The compound containing an oxime sulfonate structure represented by the general formula (b1) is also preferably an oxime sulfonate compound represented by the following general formula (b2).

(In the formula (b2), R ³¹ represents an alkyl group or an aryl group, X ¹¹ represents an alkyl group, an alkoxy group, or a halogen atom, m11 represents an integer of 0 to 3, and m11 represents 2 Or when it is 3, the plurality of X ¹¹ may be the same or different.)

The alkyl group as X ¹¹ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkoxy group as X ¹¹ is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
The halogen atom as X ¹¹ is preferably a chlorine atom or a fluorine atom.
m11 is preferably 0 or 1.
In the general formula (b2), m11 is 1, X ¹¹ is a methyl group, the substitution position of X ¹¹ is an ortho position, R ³¹ is a linear alkyl group having 1 to 10 carbon atoms, 7, A compound which is a 7-dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferable.

  The compound containing the oxime sulfonate structure represented by the general formula (b1) is more preferably an oxime sulfonate compound represented by the following general formula (B3).

(In formula (b3), R ⁴³ has the same meaning as R ⁴² in formula (b1), and X ¹ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, cyano A group or a nitro group, and n4 represents an integer of 0 to 5.)

R ⁴³ in the general formula (B3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group. Perfluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and n-octyl group is particularly preferable.
X ¹ is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
As n4, 0-2 are preferable and 0-1 are especially preferable.

  Specific examples of the compound represented by the general formula (B3) include α- (methylsulfonyloxyimino) benzyl cyanide, α- (ethylsulfonyloxyimino) benzyl cyanide, α- (n-propylsulfonyloxyimino). ) Benzyl cyanide, α- (n-butylsulfonyloxyimino) benzyl cyanide, α- (4-toluenesulfonyloxyimino) benzyl cyanide, α-[(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-butylsulfonyloxyimino) -4- Methoxyphenyl] acetonitrile, α-[(4- Toluene sulfonyl) -4-methoxyphenyl] can be mentioned acetonitrile.

  Specific examples of preferred oxime sulfonate compounds include the following compounds (i) to (viii) and the like, and these can be used alone or in combination of two or more. Compounds (i) to (viii) can be obtained as commercial products. Moreover, it can also be used in combination with another kind of (B) photo-acid generator.

  The compound containing an oxime sulfonate structure represented by the general formula (b1) is also preferably a compound represented by the following general formula (OS-1).

In the general formula (OS-1), R ¹⁰¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or Represents a heteroaryl group. ^R102 represents an alkyl group or an aryl group.
X ¹⁰¹ represents —O—, —S—, —NH—, —NR ¹⁰⁵ —, —CH ₂ —, —CR ¹⁰⁶ H—, or —CR ¹⁰⁵ R ¹⁰⁷ —, wherein R ^{105 to} R ¹⁰⁷ are alkyl groups. Or an aryl group.
R ^{121 to} R ¹²⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, Or an aryl group is represented. Two of R ^{121 to} R ¹²⁴ may be bonded to each other to form a ring.
As R ^{121 to} R ¹²⁴ , a hydrogen atom, a halogen atom, and an alkyl group are preferable, and an embodiment in which at least two of R ^{121 to} R ¹²⁴ are bonded to each other to form an aryl group is also preferable. Among these, an embodiment in which R ^{121 to} R ¹²⁴ are all hydrogen atoms is preferable from the viewpoint of sensitivity.
Any of the aforementioned functional groups may further have a substituent.

  The compound represented by the general formula (OS-1) is more preferably a compound represented by the following general formula (OS-2).

In the general formula (OS-2), R ¹⁰¹ , R ¹⁰² , R ^{121 to} R ¹²⁴ are respectively synonymous with those in the formula (OS-1), and preferred examples are also the same.
Among these, an embodiment in which R ¹⁰¹ in the general formula (OS-1) and the general formula (OS-2) is a cyano group or an aryl group is more preferable, and is represented by the general formula (OS-2). And R ¹⁰¹ is most preferably a cyano group, a phenyl group, or a naphthyl group.

  In the oxime sulfonate compound, the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.

  Specific examples of the compound represented by the general formula (OS-1) that can be suitably used in the present invention include compounds described in paragraphs [0128] to [0132] of JP2011-221494A ( Exemplified compounds b-1 to b-34) are exemplified, but the present invention is not limited thereto.

  In the present invention, the compound containing the oxime sulfonate structure represented by the general formula (b1) is represented by the following general formula (OS-3), the following general formula (OS-4) or the following general formula (OS-5). It is preferable that it is an oxime sulfonate compound represented by these.

(In the general formula (OS-3) to general formula (OS-5), R ²² , R ²⁵ and R ²⁸ each independently represents an alkyl group, an aryl group or a heteroaryl group, and R ²³ , R ²⁶ and R ²⁹ Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. X ^{1 to} X ³ each independently represents an oxygen atom or a sulfur atom, n ^{1 to} n ³ each independently represents 1 or 2, and m ^{1 to} m ³ each independently represents an integer of 0 to 6 Represents.)

In the general formulas (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group in R ²² , R ²⁵ and R ²⁸ may have a substituent.
In the above formulas (OS-3) to (OS-5), the alkyl group in R ²² , R ²⁵ and R ²⁸ is an alkyl group having 1 to 30 carbon atoms which may have a substituent. Is preferred.

In the general formulas (OS-3) to (OS-5), as the aryl group in R ²² , R ²⁵ and R ^28, an aryl group having 6 to 30 carbon atoms which may have a substituent may be used. preferable.

Moreover, in said general formula (OS-3)-(OS-5), as heteroaryl group in R <^22> , R <^25> and R < ²⁸ >, the C4-C30 heteroaryl which may have a substituent Groups are preferred.

In the general formulas (OS-3) to (OS-5), at least one ring of the heteroaryl group in R ²² , R ²⁵ and R ²⁸ may be a heteroaromatic ring. For example, a heteroaromatic ring and benzene The ring may be condensed.

In the general formulas (OS-3) to (OS-5), R ²³ , R ²⁶ and R ²⁹ are preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group. preferable.
In the general formulas (OS-3) to (OS-5), one or two of R ²³ , R ²⁶ and R ²⁹ present in the compound are an alkyl group, an aryl group or a halogen atom. It is more preferable that one is an alkyl group, an aryl group or a halogen atom, and it is particularly preferable that one is an alkyl group and the rest is a hydrogen atom.

The alkyl group for R ²³ , R ²⁶ and R ²⁹ is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and 1 to 1 carbon atoms which may have a substituent. More preferably, it is an alkyl group of 6.

The aryl group for R ²³ , R ²⁶ and R ²⁹ is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.

In the general formulas (OS-3) to (OS-5), X ^{1 to} X ³ each independently represents O or S, and is preferably O.
In the general formulas (OS-3) to (OS-5), the ring containing X ^{1 to} X ³ as a ring member is a 5-membered ring or a 6-membered ring.
In the general formulas (OS-3) to (OS-5), n ^{1 to} n ³ each independently represent 1 or 2, and when X ^{1 to} X ³ are O, n ^{1 to} n ³ are each independently 1 is preferable, and when X ^{1 to} X ³ are S, n ^{1 to} n ³ are preferably 2 each independently.

In the general formulas (OS-3) to (OS-5), R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. Represent. Among them, R ²⁴ , R ²⁷ and R ³⁰ are preferably each independently an alkyl group or an alkyloxy group.
The alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group in R ²⁴ , R ²⁷ and R ³⁰ may have a substituent.
In the general formulas (OS-3) to (OS-5), the alkyl group in R ²⁴ , R ²⁷ and R ³⁰ is an alkyl group having 1 to 30 carbon atoms which may have a substituent. It is preferable.

In the general formulas (OS-3) to (OS-5), the alkyloxy group in R ²⁴ , R ²⁷ and R ³⁰ is an alkyloxy group having 1 to 30 carbon atoms which may have a substituent. Preferably there is.

In the general formulas (OS-3) to (OS-5), m ^{1 to} m ³ each independently represents an integer of 0 to 6, preferably an integer of 0 to 2, preferably 0 or 1. More preferably, it is particularly preferably 0.
In addition, with respect to the substituents of (OS-3) to (OS-5), (OS-3) to (OS-5) described in paragraphs [0092] to [0109] of JP2011-221494A. The preferred range of substituents of

  The compound containing the oxime sulfonate structure represented by the general formula (B1) is particularly an oxime sulfonate compound represented by any one of the following general formulas (OS-6) to (OS-11). preferable.

(In the formulas (OS-6) to (OS-11), R ^{301 to} R ³⁰⁶ represent an alkyl group, an aryl group, or a heteroaryl group, R ³⁰⁷ represents a hydrogen atom or a bromine atom, and R ^{308 to} R ³¹⁰ , R ³¹³ , R ³¹⁶ and R ³¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group; R ³¹¹ and R ³¹⁴ each independently represent a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ³¹² , R ³¹⁵ , R ³¹⁷ and R ³¹⁹ each independently represent a hydrogen atom or a methyl group.)

  Preferred ranges of the substituents in the general formulas (OS-6) to (OS-11) are described in paragraphs [0110] to [0112] of JP2011-221494A (OS-6) to ( This is the same as the preferred range of OS-11).

  Specific examples of the oxime sulfonate compound represented by the general formula (OS-3) to the general formula (OS-5) include compounds described in paragraphs [0114] to [0120] of JP2011-221494A. However, the present invention is not limited to these examples.

  In the photosensitive resin composition of the present invention, (C) the photoacid generator is added to 100 parts by weight of all resin components (preferably solid content, more preferably the (A) copolymer) in the photosensitive resin composition. On the other hand, it is preferable to use 0.1-10 weight part, and it is more preferable to use 0.5-10 weight part.

  The photosensitive resin composition of the present invention is a combination of a photoacid generator containing an oxime sulfonate structure represented by general formula (b1) and a basic compound represented by general formula (Qa) described later. It is preferable to use it.

<(D) Basic compound>
The photosensitive resin composition of the present invention contains (D) a basic compound. The basic compound (also referred to as “component (D)”) used in the present invention can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like.

Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and dicyclohexylamine. , Dicyclohexylmethylamine and the like.
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, 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 and the like.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.
The basic compounds that can be used in the present invention may be used singly or in combination of two or more. However, it is preferable to use two or more in combination, and it is more preferable to use two in combination. It is preferable to use two kinds of heterocyclic amines in combination.

In the present invention, the component (D) is preferably at least one compound represented by the following general formulas (Qa), (Qb), and (Qc).
(In the general formula (Qa), R ² represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. X represents an oxygen atom or a sulfur atom. Y ¹ represents an oxygen atom. Or -NH- group, p1 represents an integer of 1 to 3)
The component (D) used in the present invention has a structural feature that has a partial structure represented by at least one urea or thiourea bond in the molecule, and contains a morpholino group or a piperazino group. A compound.

The component (D) is preferably a thiourea compound represented by the following general formula (Q-a2) where X is a sulfur atom, that is, a partial structure represented by a thiourea bond.
(In the general formula (Q-a2), R ³ represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. Y ² represents an oxygen atom or an —NH— group. Represents an integer of 1 to 3)

More preferably, the component (D) is a thiourea compound represented by the following general formula (Q-a3), that is, contains a morpholino group.
(In the general formula (Q-a3), R ⁴ represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. P3 represents an integer of 1 to 3)

Examples of the alkyl group having 1 to 6 carbon atoms in R ^{2 to} R ⁴ of the compounds represented by the general formulas (Qa) to (Qa3) include a methyl group, an ethyl group, a propyl group, and n-butyl. C1-C4 alkyl groups, such as a group, a sec-butyl group, and a t-butyl group, are preferable, a linear C1-C4 alkyl group is more preferable, and a methyl group is especially preferable.

Examples of the cycloalkyl group having 3 to 10 carbon atoms in R ^{2 to} R ⁴ of the compounds represented by the general formulas (Qa) to (Qa3) include a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, and an adamantyl group. A cycloalkyl group having 3 to 10 carbon atoms such as cycloalkyl group having 5 to 10 carbon atoms is more preferable, and a cyclohexyl group is particularly preferable.

  Specific examples of the component (D) represented by the general formula (Qa) include the compounds (C-1) to (C-7) shown below. It is not limited.

  These components (D) can be used alone or in admixture of two or more.

In general formula (Qb), R < ⁸ >, R <^9> , R < ¹⁰ > has a hydrogen atom and the C1-C6 alkyl group which may have a substituent, and a substituent each independently. Or an aryl group which may be substituted or a cycloalkyl group having 3 to 10 carbon atoms which may have a substituent.

Examples of the alkyl group or aryl group having 1 to 6 carbon atoms in R ^{8 to} R ¹⁰ of the compound represented by the general formula (Qb) include a methyl group, an ethyl group, a propyl group, an n-butyl group, sec -A butyl group, a t-butyl group, a pentyl group, a neopentyl group, a hexyl group and the like are preferable, a linear alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group is particularly preferable.

Examples of the cycloalkyl group having 3 to ¹⁰ carbon atoms in R ^{8 to} R ¹⁰ of the compound represented by the general formula (Qb) include 3 to 3 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, and an adamantyl group. A cycloalkyl group having 10 carbon atoms is preferable, a cycloalkyl group having 5 to 10 carbon atoms is more preferable, and a cyclohexyl group is particularly preferable.

Examples of the substituent that the alkyl group and aryl group in R ^{8 to} R ¹⁰ of the compound represented by the general formula (Qb) may have include an alkyl group of R ^{3 in} the general formula (I). It is the same as the preferable substituent which can be made.

  In the present invention, the addition amount of the component (D) is all resin components (preferably solid content, more preferably the component (A) in the photosensitive resin composition, from the viewpoint of satisfying all of sensitivity and resolution. It is usually used in the range of 0.001 to 20% by weight based on the copolymer), preferably 0.005 to 10% by weight, and most preferably 0.01 to 5% by weight.

<(E) Solvent>
The photosensitive resin composition of the present invention contains (E) a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution in which the components (A) to (D), which are essential components, and other components described below are dissolved in a solvent (E).
As the solvent (E) used in the photosensitive resin composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene. Glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol Examples include monoalkyl ether acetates, esters, ketones, amides, lactones and the like.

Specific examples of the solvent (E) used in the photosensitive resin composition of the present invention include the solvents described in paragraphs [0174] to [0178] of JP2011-221494A, for example.
In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonal as necessary for these solvents , Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added. These solvents can be used alone or in combination of two or more. The solvent that can be used in the present invention is a single type or a combination of two types, more preferably a combination of two types, propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates. And diethylene glycol dialkyl ethers or esters and butylene glycol alkyl ether acetates are more preferably used in combination.

The component (E) is preferably a solvent having a boiling point of 130 ° C. or more and less than 160 ° C., a solvent having a boiling point of 160 ° C. or more, or a mixture thereof, a solvent having a boiling point of 130 ° C. or more and less than 160 ° C., and a boiling point of 160 ° C. A solvent having a boiling point of 200 ° C. or lower or a mixture thereof is more preferable, and a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C. and a solvent having a boiling point of 160 ° C. or higher and 200 ° C. or lower is still more preferable.
Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
Solvents having a boiling point of 160 ° C. or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C.), diethylene glycol methyl ethyl ether (boiling point 176 ° C.), propylene glycol monomethyl ether propionate (boiling point 160 ° C.), dipropylene glycol methyl ether acetate. (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butylene glycol diacetate (boiling point 232 ° C) It can be.

  The content of the solvent (E) in the photosensitive resin composition of the present invention is based on 100 parts by weight of all resin components (preferably solid content, more preferably the (A) copolymer) in the photosensitive resin composition. The amount is preferably 50 to 3,000 parts by weight, more preferably 100 to 2,000 parts by weight, and even more preferably 150 to 1,500 parts by weight.

<Other ingredients>
In addition to the component (A), the component (B), the component (C), the component (D) and the component (E), the positive photosensitive resin composition of the present invention includes (N) as necessary. A sensitizer, (G) an adhesion improver, (I) a surfactant, and (J) an antioxidant can be preferably added. Further, the positive photosensitive resin composition of the present invention includes a plasticizer, a thermal radical generator, an antioxidant, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor. Known additives can be added.

(N) Sensitizer The photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote its decomposition in combination with (C) a photoacid generator. The sensitizer absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.

Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene), xanthenes (Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine oleoresin) Di, chloroflavin, acriflavine), acridones (eg, acridone, 10-butyl-2-chloroacridone), anthraquinones (eg, anthraquinone), squariums (eg, squalium), styryls, base styryls ( For example, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (for example, 7-diethylamino 4-methylcoumarin, 7-hydroxy-4-methylcoumarin, 2,3,6,7 -Tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolizine-11-non).
Among these sensitizers, polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable. Of the polynuclear aromatics, anthracene derivatives are most preferred.

(G) Adhesion improving agent The photosensitive resin composition of the present invention may contain (G) an adhesion improving agent. The adhesion improver (G) that can be used in the photosensitive resin composition of the present invention includes an inorganic substance serving as a substrate, for example, a silicon compound such as silicon, silicon oxide, and silicon nitride, a metal such as gold, copper, and aluminum. It is a compound that improves adhesion to an insulating film. Specific examples include silane coupling agents and thiol compounds. The silane coupling agent (G) used as an adhesion improver used in the present invention is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.
Preferred silane coupling agents include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ- Methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltri An alkoxysilane is mentioned. Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is more preferable. Further preferred. These can be used alone or in combination of two or more. These are effective in improving the adhesion to the substrate and are also effective in adjusting the taper angle with the substrate.
The content of the (G) adhesion improving agent in the photosensitive resin composition of the present invention is 100 parts by weight of all resin components (preferably solid content, more preferably (A) copolymer) in the photosensitive resin composition. The amount is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight.

(I) Surfactant The photosensitive resin composition of the present invention may contain (I) a surfactant. (I) As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by JEMCO), MegaFac (manufactured by DIC Corporation), Florard (Sumitomo 3M) (Made by Co., Ltd.), Asahi Guard, Surflon (made by Asahi Glass Co., Ltd.), PolyFox (made by OMNOVA), and the like.
In addition, as a surfactant, it contains a structural unit A and a structural unit B represented by the following general formula (1), and is a weight average in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. A preferred example is a copolymer having a molecular weight (Mw) of 1,000 to 10,000.

(In Formula (1), R ⁴⁰¹ and R ⁴⁰⁴ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or 1 carbon atom. Represents an alkyl group having ˜4, L represents an alkylene group having 3 to 6 carbon atoms, p and q are weight percentages representing a polymerization ratio, p represents a numerical value of 10 wt% to 80 wt%, and q is (A numerical value of 20% by weight to 90% by weight is represented, r represents an integer of 1 to 18, and s represents an integer of 1 to 10.)

The L is preferably a branched alkylene group represented by the following general formula (2). R ⁴⁰⁵ in the general formula (2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. The alkyl group is more preferable. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by weight.

General formula (2)

  As for the weight average molecular weight (Mw) of the said copolymer, 1,500-5,000 are more preferable.

These surfactants can be used individually by 1 type or in mixture of 2 or more types.
The amount of (I) surfactant added in the photosensitive resin composition of the present invention is 100 weights of all resin components (preferably solid content, more preferably (A) copolymer) in the photosensitive resin composition. The amount is preferably 10 parts by weight or less, more preferably 0.01 to 10 parts by weight, and still more preferably 0.01 to 1 part by weight with respect to parts.

(J) Antioxidant The photosensitive resin composition of the present invention may contain an antioxidant. As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat-resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites. Examples thereof include salts, thiosulfates, and hydroxylamine derivatives. Among these, a phenolic antioxidant is particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness. These may be used alone or in combination of two or more.

  As a commercial item of a phenolic antioxidant, ADK STAB AO-60, ADK STAB AO-80 (above, the product made from ADEKA), and Irganox 1098 (made by Ciba Japan Co., Ltd.) are mentioned, for example.

The content of the antioxidant is preferably 0.1 to 6% by weight, more preferably 0.2 to 5% by weight, based on the total solid content of the photosensitive resin composition. It is particularly preferably 5 to 4% by weight. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation becomes good.
As additives other than antioxidants, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like are used in the present invention. You may add to a resin composition.

[Pattern manufacturing method]
Next, the pattern manufacturing method of the present invention will be described.
The pattern manufacturing method of the present invention includes the following steps (1) to (6).
(1) The process of applying the photosensitive resin composition of this invention on a board | substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) a step of exposing with actinic radiation,
(4) a step of developing with an aqueous developer,
(5) etching the substrate using the formed resist pattern as a mask, and
(6) A step of removing the resist pattern.
Each step will be described below in order.

In the step (1), the positive photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent.
In the step (2), the solvent is removed from the applied film by decompression (vacuum) and / or heating to form a dry coating film on the substrate.

  (3) In the exposing step, the obtained coating film is irradiated with actinic rays having a wavelength of 300 nm to 450 nm. In this step, (C) the photoacid generator is decomposed to generate an acid. Due to the catalytic action of the generated acid, the protected hydroxy group of the monomer unit (a1) of hydroxystyrene contained in the component (A) is hydrolyzed to produce a phenolic hydroxyl group.

  In order to accelerate the hydrolysis reaction in the region where the acid catalyst is generated, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as “PEB”) can be performed as necessary. PEB can promote the formation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The pattern production method of the present invention preferably includes a step of post-baking and thermosetting the resist pattern after the development step and before the etching step.

In the present invention, the protected hydroxy group of the monomer unit (a1) of hydroxystyrene contained in the component (A) has a low activation energy for acid decomposition, and is easily decomposed by an acid derived from an acid generator by exposure, Since a phenolic hydroxyl group is generated, a positive image can be formed by development without necessarily performing PEB. However, in the method for producing a pattern of the present invention, the above-described post-baking is performed using the photosensitive resin composition of the present invention. It is preferable to perform a process.
In the pattern production method of the present invention, it is preferable to promote hydrolysis of acid-decomposable groups without causing a crosslinking reaction by performing PEB at a relatively low temperature. The temperature for performing PEB is preferably 30 ° C to 130 ° C, more preferably 40 ° C to 110 ° C, and particularly preferably 50 ° C to 100 ° C. The heating time can be appropriately set depending on the heating temperature or the like, but is preferably in the range of 1 to 60 minutes.

(4) In the developing step, the copolymer having a liberated carboxyl group or phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing an exposed area containing a resin composition having a carboxyl group or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.
By performing PEB at a relatively low temperature, it is preferable to promote hydrolysis of the acid-decomposable group without causing a crosslinking reaction. The temperature for performing PEB is preferably 30 ° C to 130 ° C, more preferably 40 ° C to 110 ° C, and particularly preferably 50 ° C to 80 ° C. The heating time can be appropriately set depending on the heating temperature or the like, but is preferably in the range of 10 to 90 minutes.
In the pattern manufacturing method of the present invention, it is preferable that a post-baking step is included between (4) the developing step and an etching step described later, and (4) the resist pattern after the developing step and before the etching step. It is more preferable to include a step of post-baking at 100 to 160 ° C. (4) By heating the obtained positive image in the post-baking step after the developing step, the effect of improving etching dimensional stability can be obtained.
The post-baking step after the step (4) developing and before the step (5) etching is more preferably 120 to 150 ° C. By performing PEB at a relatively low temperature, an effect of improving etching dimensional stability without causing heat flow of the resist pattern can be obtained.
The heating time can be appropriately set depending on the heating temperature or the like, but is preferably in the range of 1 to 60 minutes.
Next, the formation method of the cured film using the photosensitive resin composition of this invention is demonstrated concretely.

<Method for preparing photosensitive resin composition>
The essential components (A) to (E) are mixed at a predetermined ratio and in an arbitrary manner, and dissolved by stirring to prepare a photosensitive resin composition. For example, the resin composition can also be prepared by mixing the components (A) to (D) with a solution obtained by dissolving the components (E) in advance in the solvent (E) in a predetermined ratio. The composition solution prepared as described above can be used after being filtered using a filter having a pore size of 0.2 μm or the like.

<(1) Step of applying photosensitive resin composition on substrate and (2) Step of removing solvent>
A desired dry coating film can be formed by applying the photosensitive resin composition to a predetermined substrate and removing the solvent by decompression and / or heating (pre-baking). Examples of the substrate include, for example, a glass plate in which a polarizing plate, a black matrix layer and a color filter layer are provided as necessary, and a transparent conductive circuit layer is further provided in the production of a liquid crystal display element. Although there is no restriction | limiting in particular as a method of applying the photosensitive resin composition to a board | substrate, Among these, it is preferable to apply | coat a touristic resin composition to a board | substrate in this invention. The coating method to a board | substrate is not specifically limited, For example, methods, such as a slit coat method, a spray method, a roll coat method, a spin coat method, can be used. Among them, the slit coating method is preferable from the viewpoint of being suitable for a large substrate. Manufacturing with a large substrate is preferable because of high productivity. Here, the large substrate means a substrate having a side of 1 m or more on each side.

  Further, the heating condition in the step (2) is a range in which the acid-decomposable group is decomposed in the monomer unit (a1) in the component (A) in the unexposed area and the component (A) is not soluble in the alkali developer. Although it varies depending on the type and blending ratio of each component, it is preferably about 80 to 130 ° C. for 30 to 120 seconds.

<(3) Step of exposing and (4) Step of developing (pattern forming method)>
In the step (3), the substrate provided with the coating film is irradiated with actinic rays through a mask having a predetermined pattern. After the exposure step, heat treatment (PEB) is performed as necessary, and then in step (4), an exposed area is removed using an alkaline developer to form an image pattern.
For exposure with actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, or the like can be used, and g-line (436 nm), i-line (365 nm), h-line (405 nm). Actinic rays having a wavelength of 300 nm to 450 nm such as) can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
As the mask used in the step (3), it is preferable to use a halftone phase mask capable of obtaining a pattern having a plurality of thicknesses at a time.

  The developer used in the step (4) preferably contains a basic compound. Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.

The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 180 seconds, and the development method may be any of a liquid piling method, a dip method, and the like. After the development, washing with running water is performed for 30 to 90 seconds, and a desired pattern can be formed.

<(5) Step of etching>
The pattern manufacturing method of the present invention includes the step (5) of etching the substrate using the formed resist pattern as a mask.
There is no restriction | limiting in particular as a method of etching the said board | substrate using the said resist pattern as a mask, A well-known method can be used.

<(6) Step of peeling resist pattern>
The pattern production method of the present invention includes the step (6) of peeling the resist pattern.
There is no restriction | limiting in particular as a peeling method of the said resist pattern, A well-known method can be used.

<Board>
The substrate used in the pattern manufacturing method of the present invention is not particularly limited. For example, a chromium film, a molybdenum film, a molybdenum alloy film, a tantalum film, a tantalum alloy film, an indium oxide (ITO) film doped with tin oxide, or tin oxide. Film, Ni, Cu, Fe, Al, etc. metal substrate; quartz, glass, silicon nitride film, silicone, silicone nitride, polysilicone, silicone oxide, amorphous silicone film, SOG, silicon wafer for semiconductor device manufacturing, liquid crystal device manufacturing Silicon substrates such as glass square substrates for use; paper, polyester film, polycarbonate film, polyimide film, polymer substrates such as other polymer substrates used in organic EL display devices; ceramic materials, Ti substrates, Al substrates, etc. may be used it can. Among them, in the present invention, an ITO substrate, a molybdenum substrate or a silicon substrate is preferable, and an ITO substrate is more preferable.
The shape of the substrate may be a plate shape or a roll shape.

[Curing film]
In the present invention, (4) after the developing step, the pattern corresponding to the unexposed area obtained by development is predetermined at a predetermined temperature, for example, 180 to 250 ° C., using a heating device such as a hot plate or an oven. For example, 5 to 60 minutes on a hot plate and 30 to 90 minutes on an oven to form a cured film such as a protective film or an interlayer insulating film having excellent heat resistance and hardness. Can do.
Moreover, when performing heat processing, transparency of a cured film can also be improved by performing in nitrogen atmosphere.
Prior to the heat treatment, it is preferable that the substrate having the cured film formed in a pattern is re-exposed with actinic rays and then heated.

That is, in order to form the cured film of the present invention, it is preferable to include a step of re-exposing with actinic rays between the developing step and the thermosetting step.
The exposure in the re-exposure step may be performed by the same means as in the exposure step. However, in the re-exposure step, the entire surface of the substrate on which the film is formed by the photosensitive resin composition of the present invention is used. It is preferable to perform exposure. A preferable exposure amount for the re-exposure step is 100 to 1,000 mJ / cm ² .

[pattern]
The pattern of this invention is a pattern obtained by etching the said board | substrate using the resist pattern obtained by hardening | curing the photosensitive resin composition of this invention as a mask. The pattern of the present invention can be preferably used as an ITO pattern, a molybdenum pattern or a silicon pattern, and more preferably used as an ITO pattern.
Since the photosensitive resin composition of the present invention is excellent in sensitivity, resolution and exposure margin, a resist pattern having excellent rectangularity can be obtained. Since the pattern of the present invention is obtained by the method for producing a pattern of the present invention using the resist pattern, it can be finely processed, and an organic EL display device or a liquid crystal display device can have high definition display characteristics.

[Organic EL display device, Liquid crystal display device]
The photosensitive resin composition of the present invention can also be used as an interlayer insulating film, and an organic EL display device and a liquid crystal display device can be manufactured by the pattern manufacturing method of the present invention. The organic EL display device and the liquid crystal display device of the present invention preferably have an ITO pattern.
The organic EL display device or liquid crystal display device of the present invention is not particularly limited except that it has a planarizing film or an interlayer insulating film formed using the photosensitive resin composition of the present invention, and has various structures. Various known organic EL display devices and liquid crystal display devices can be used.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.

FIG. 1 is a conceptual diagram illustrating an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening layer 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 1, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a first layer made of Al is formed on the entire surface above the substrate. An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving the organic EL element. An EL display device is obtained.

  FIG. 2 is a conceptual cross-sectional view showing an example of the active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on weight.

(Synthesis Example 1: Synthesis of Polymer A1-1)
20 g of alkali-soluble resin (Marcalinker MS-4P manufactured by Maruzen Petrochemical Co., Ltd.) and 320 g of propylene glycol monomethyl ether acetate (PGMEA) were dissolved in a flask and distilled under reduced pressure, and water and PGMEA were distilled off azeotropically. After confirming that the water content was sufficiently low, 4.48 g of ethyl vinyl ether and 0.35 g of p-toluenesulfonic acid were added and stirred at room temperature for 1 hour. Thereto, 0.28 g of triethylamine was added to stop the reaction. After adding ethyl acetate to the reaction solution and further washing with water, ethyl acetate, water and azeotropic PGMEA were distilled off by distillation under reduced pressure to obtain polymer A1-1 which is an alkali-soluble resin protected with an acid-decomposable group. Obtained. The weight average molecular weight of the obtained resin was 11,000. The polydispersity was 2.6.
The structure of the polymer A1-1 is a 1-ethoxyethyl protected body of p-hydroxystyrene / p-hydroxystyrene copolymer (30 mol% / 70 mol%).

(Synthesis Example 2: Synthesis of Polymer A1-2)
In Synthesis Example 1, polymer A1-2 was obtained in the same manner as in Synthesis Example 1 except that the addition amount of ethyl vinyl ether was changed and the protection rate was changed to 40%.
The structure of polymer A1-2 is a 1-ethoxyethyl protector / p-hydroxystyrene copolymer (40 mol% / 60 mol%) of p-hydroxystyrene. The polydispersity was 2.6 and Mw was 11000.

(Synthesis Example 3: Synthesis of Polymer A1-3)
A polymer A1-3 was obtained in the same manner as in Synthesis Example 1 except that 4.48 g of ethyl vinyl ether was replaced with 3.61 g of methyl vinyl ether in Synthesis Example 1.
The structure of the polymer A1-3 is a 1-methoxyethyl group protected body of p-hydroxystyrene / p-hydroxystyrene copolymer (30 mol% / 70 mol%). The polydispersity was 2.6 and Mw was 11000.

(Synthesis Example 4: Synthesis of Polymer A1-4)
A polymer A1-4 was obtained in the same manner as in Synthesis Example 1 except that 4.48 g of ethyl vinyl ether was replaced with 5.35 g of propyl vinyl ether in Synthesis Example 1.
The structure of polymer A1-4 is a 1-propoxyethyl group protected body of p-hydroxystyrene / p-hydroxystyrene copolymer (30 mol% / 70 mol%). The polydispersity was 2.6 and Mw was 11000.

(Synthesis Example 5: Synthesis of Polymer A1-5)
Polymer A1-5 was obtained in the same manner as in Synthesis Example 1 except that 4.48 g of ethyl vinyl ether was replaced with 6.22 g of tertiary butyl vinyl ether in Synthesis Example 1.
The structure of the polymer A1-5 is a 1-t-butoxyethyl group protector of p-hydroxystyrene / p-hydroxystyrene copolymer (30 mol% / 70 mol%). The polydispersity was 2.6 and Mw was 11000.

(Synthesis Example 6: Synthesis of Polymer A1-6)
Polymer A1-6 was obtained in the same manner as in Synthesis Example 1 except that 4.48 g of ethyl vinyl ether was replaced with 7.84 g of cyclohexyl vinyl ether in Synthesis Example 1.
The structure of the polymer A1-6 is a 1-cyclohexyloxyethyl group protected product of p-hydroxystyrene / p-hydroxystyrene copolymer (30 mol% / 70 mol%). The polydispersity was 2.6 and Mw was 12000.

(Synthesis Example 7: Synthesis of Polymer A1-7)
Polymer A1-7 was synthesized in the same manner as in Synthesis Example 1 except that the alkali-soluble resin (Marcalinker MS-4P: manufactured by Maruzen Chemical Industry Co., Ltd.) was replaced with VP-15000 (manufactured by Nippon Soda Co., Ltd.) in Synthesis Example 1. Got.
Polymer A1-7 had a polydispersity of 1.05 and Mw of 20000.

(Synthesis Example 8: Synthesis of Polymer A1-8)
In Synthesis Example 1, polymer A1-8 was obtained in the same manner as in Synthesis Example 1 except that the addition amount of ethyl vinyl ether was changed and the protection rate was changed to 40%.
The structure of polymer A1-8 is a 1-ethoxyethyl protector / p-hydroxystyrene copolymer of p-hydroxystyrene (30 mol% / 70 mol%). The polydispersity was 1.1 and Mw was 24,000.

(Synthesis Example 9: Synthesis of Polymer A1-9)
In Synthesis Example 1, the same procedure as in Synthesis Example 1 was conducted except that the alkali-soluble resin (Marcalinker MS-4P: manufactured by Maruzen Chemical Industry Co., Ltd.) was replaced with Marcalinker MH-2P (manufactured by Maruzen Petrochemical Co., Ltd.). Polymer A1-9 was obtained.
Polymer A1-9 had a polydispersity of 5.7 and Mw of 24,000.

(Synthesis Example 10: Synthesis of Polymer A2-1)
15.6 g of alkali-soluble resin (Marcalinker MS-4P: manufactured by Maruzen Chemical Industry Co., Ltd.) and 100 g of propylene glycol monomethyl ether acetate (PGMEA) are dissolved in a flask and distilled under reduced pressure to azeotropically distill water and PGMEA. Left. After confirming that the water content was sufficiently low, 2.7 g of 2,3-dihydrofuran and 0.015 g of p-toluenesulfonic acid were added and stirred at room temperature for 2 hours. Thereto was added 0.090 g of triethylamine to stop the reaction. Ethyl acetate was added to the reaction solution, and the mixture was further washed with water. Then, ethyl acetate and water were distilled off under reduced pressure to obtain polymer A2-1 which is a soluble resin having a protection rate of 25 mol%. The weight average molecular weight of the obtained resin was 12,000. The polydispersity was 2.6.
The structure of the polymer A2-1 is a 2-tetrahydrofuranyl protected product of p-hydroxystyrene / p-hydroxystyrene copolymer (25 mol% / 75 mol%).

(Synthesis Example 11: Synthesis of Polymer A2-2)
In Synthesis Example 10, polymer A2-2 was obtained in the same manner as in Synthesis Example 10 except that the amount of 2,3-dihydrofuran added was changed to 4.3 g and the protection rate was changed to 40%.
The structure of the polymer A2-2 is a 2-tetrahydrofuranyl protected product of p-hydroxystyrene / p-hydroxystyrene copolymer (40 mol% / 60 mol%). The polydispersity was 2.6 and Mw was 12000.

(Synthesis Example 12: Synthesis of Polymer A2-3)
Polymer A2-3 was obtained in the same manner as in Synthesis Example 10 except that 2.7 g of 2,3-dihydrofuran in Synthesis Example 10 was replaced with 3.97 g of 2,3-dimethyl-2,3-dihydrofuran.
The structure of polymer A2-3 is a 3,4-dimethyl-2-tetrahydrofuranyl protector / p-hydroxystyrene copolymer (25 mol% / 75 mol%) of p-hydroxystyrene. The polydispersity was 2.6 and Mw was 12000.

(Synthesis Example 13: Synthesis of Polymer A2-4)
In the same manner as in Synthesis Example 10 except that 2.7 g of 2,3-dihydrofuran was replaced with 5.02 g of 1-oxabicyclo [4,2,0] hepta-2,3-ene in Synthesis Example 10, Polymer A2 -4 was obtained.
The structure of polymer A2-4 is a protected body of 2-tetrahydrofuranyl derivative of p-hydroxystyrene / p-hydroxystyrene copolymer (25 mol% / 75 mol%). The polydispersity was 2.6 and Mw was 12000.

(Synthesis Example 14: Synthesis of Polymer A2-5)
A polymer A2-5 was obtained in the same manner as in Synthesis Example 10, except that 2.7 g of 2,3-dihydrofuran in Synthesis Example 10 was replaced with 8.98 g of 2,3-diphenyl-2,3-dihydrofuran.
The structure of polymer A2-5 is 3,4-diphenyl-2-tetrahydrofuranyl protected / p-hydroxystyrene copolymer (25 mol% / 75 mol%) of p-hydroxystyrene. The polydispersity was 2.6 and Mw was 12000.

(Synthesis Example 15: Synthesis of Polymer A2-6)
In the same manner as in Synthesis Example 10 except that 2.7 g of 2,3-dihydrofuran was replaced with 2.83 g of 2-methyl-2,3-dihydro-furan in Synthesis Example 10, Polymer A2-6 was obtained.
The structure of polymer A2-6 is a 3-methyl-2-tetrahydrofuranyl protector / p-hydroxystyrene copolymer (25 mol% / 75 mol%) of p-hydroxystyrene. The polydispersity was 2.6 and Mw was 12000.

(Synthesis Example 16: Synthesis of Polymer A2-7)
Polymer A2-7 was synthesized in the same manner as in Synthesis Example 10 except that the alkali-soluble resin (Marcalinker MS-4P: manufactured by Maruzen Chemical Industry Co., Ltd.) was replaced with VP-15000 (manufactured by Nippon Soda Co., Ltd.) in Synthesis Example 10. Got.
Polymer A2-7 had a polydispersity of 1.10 and Mw of 21,000.

(Synthesis Example 17: Synthesis of Polymer A2-8)
In Synthesis Example 10, polymer A2-8 was prepared in the same manner as in Synthesis Example 10 except that the alkali-soluble resin (Marcalinker MS-4P: manufactured by Maruzen Chemical Industry Co., Ltd.) was replaced with VP-15000 (manufactured by Nippon Soda Co., Ltd.). Got.
Polymer A2-8 had a polydispersity of 1.10 and Mw of 21,000.

(Synthesis Example 18: Synthesis of Polymer A2-9)
In Synthesis Example 10, the same procedure as in Synthesis Example 10 was conducted except that the alkali-soluble resin (Marcalinker MS-4P: manufactured by Maruzen Chemical Industry Co., Ltd.) was replaced with Marcalinker MH-2P (manufactured by Maruzen Petrochemical Co., Ltd.). Polymer A2-9 was obtained.
Polymer A2-9 had a polydispersity of 5.6 and Mw of 24,000.

(Synthesis Example 19: Synthesis of Polymer A4)
15.6 g of alkali-soluble resin (Marcalinker MS-4P, manufactured by Maruzen Petrochemical Co., Ltd.) and 100 g of propylene glycol monomethyl ether acetate (PGMEA) are dissolved in a flask and distilled under reduced pressure to azeotropically distill water and PGMEA. did. After confirming that the water content was sufficiently low, 3.4 g of 2,3-dihydropyran and 0.015 g of p-toluenesulfonic acid were added and stirred at room temperature for 2 hours. Thereto was added 0.10 g of triethylamine to stop the reaction. Ethyl acetate was added to the reaction solution, and the mixture was further washed with water. Then, ethyl acetate and water were distilled off under reduced pressure to obtain polymer A4 which is a soluble resin having a protection rate of 25 mol%. The weight average molecular weight of the obtained resin was 12,000. The polydispersity was 2.6.
The structure of polymer A4 is a 2-tetrahydropyranyl protector / p-hydroxystyrene copolymer of p-hydroxystyrene (25 mol% / 75 mol%).

(Adjustment of photosensitive resin composition)
Each component was dissolved and mixed so that it might become a composition shown in the following table | surface, and it filtered with the filter made from a polytetrafluoroethylene with a diameter of 0.2 micrometer, and obtained the photosensitive resin composition of an Example and a comparative example. The blending ratio was as shown in the following table.
-(A) Polymer component (A1) The polymer and (A2) polymer were blended in the proportions shown in the following table.
-(B) Parahydroxystyrene resin (A) It mix | blended with the ratio (weight% described in a table | surface) as described in a table | surface with respect to 100 weight part of polymers.
・ (C) Acid generator (A) 2.7 parts by weight with respect to 100 parts by weight of polymer ・ (D) Basic compound (A) 0.2 parts by weight with respect to 100 parts by weight of polymer In this case, (A) 2.7 parts by weight with respect to 100 parts by weight of the polymer, surfactant (A) 0.1 parts by weight with respect to 100 parts by weight of the polymer, and the solvent PGMEA nonvolatile content is 10% by weight with respect to the resist solution. Adjust to be

C-1: CGI-1397 (Ciba Specialty Chemicals)

<Synthesis of C-2>
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 ° C. for 2 hours. I let you. Under ice-cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added for liquid separation. Potassium carbonate (19.2 g) was added to the organic layer, reacted at 40 ° C. for 1 hour, 2N HCl aqueous solution (60 mL) was added and separated, and the organic layer was concentrated, and the crystals were diluted with diisopropyl ether (10 mL). The slurry was reslurried, filtered and dried to obtain a ketone compound (6.5 g).
Acetic acid (7.3 g) and 50% by weight hydroxylamine aqueous solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (30 mL), and the mixture was heated to reflux. After allowing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).
The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the temperature was raised to room temperature. Reacted for hours. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, then reslurried with methanol (20 mL), filtered, and dried to obtain 2.3 g of C-2.
The ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of C-2 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7. 8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (q, 1H) , 2.4 (s, 3H), 1.7 (d, 3H).

<Synthesis of C-3>
Α- (p-Toluenesulfonyloxyimino) phenylacetonitrile (Compound C-3) was synthesized according to the method described in paragraph No. [0108] of JP-T-2002-528451.

C-4: (Product name: TPS-1000, manufactured by Midori Chemical Co., Ltd.)

DBA (trade name, 9,10-dibutoxyanthracene, manufactured by Kawasaki Chemical Industries)

Q-1: (trade name CMTU, manufactured by Toyo Kasei Kogyo Co., Ltd.)

Q-2: (Product name T0999, manufactured by Tokyo Chemical Industry Co., Ltd.)

Q-3: (trade name D131, manufactured by Tokyo Chemical Industry Co., Ltd.)

VP-15000: (trade name VP-15000, manufactured by Nippon Soda Co., Ltd.)

VP-8000: (Brand name VP-8000, manufactured by Nippon Soda Co., Ltd.)

S-1: (trade name Marca Linker MS-1P, manufactured by Maruzen Chemical Industry Co., Ltd.)

S-2: (trade name Marca Linker M S-2P, manufactured by Maruzen Chemical Industry Co., Ltd.)

S-4: (Brand name Marcalinker MS-4P, manufactured by Maruzen Chemical Industry Co., Ltd.)

H-2: (trade name Marca Linker MH-2P, manufactured by Maruzen Chemical Industry Co., Ltd.)

Surfactant: Perfluoroalkyl group-containing nonionic surfactant shown below

  Each evaluation shown below was performed about the photosensitive resin composition of each Example obtained by the above and each comparative example.

<Evaluation of sensitivity>
A photosensitive resin composition with a film thickness of 1.3 μm is applied to a glass substrate that has been cleaned and treated with HMDS (hexamethyldisilazane), exposed to light through a mask, and an exposure amount at which a 10 μm line and space pattern becomes exactly 10 μm The sensitivity was evaluated with the optimal exposure amount.
1 point: An exposure amount of 100 mJ / cm ² or more is required 2 points: An exposure amount of 50 mJ / cm ² or more is required 3 points: An exposure amount of 20 mJ / cm ² or more is required 4 points: 10 mJ / cm ² or more 20 mJ / cm Exposure amount less than ² 5 points: Exposure amount less than 10 mJ / cm ²

<Evaluation of resolution>
A photosensitive resin composition having a film thickness of 1.3 μm was applied to a glass substrate that had been cleaned and treated with HMDS, and was exposed and developed through a mask.
1 point: resolution 5 μm or more 2 points: 3.0 μm resolves but 2.5 μm does not resolve 3 points: 2.5 μm resolves but 2.0 μm does not resolve 4 points: 2.0 μm Resolved but 1.5 μm not resolved 5 points: 1.5 μm resolved.

<Evaluation of line width sensitivity (PED)>
A photosensitive resin composition with a film thickness of 1.3 μm is applied to a glass substrate that has been cleaned and treated with HMDS, exposed and developed through a mask, and the space width of the 2.5 μm line-and-space pattern portion is from exposure to development. The fluctuation range (μm) that fluctuates between 2 minutes and 30 minutes was evaluated as PED.
1 point: fluctuation range of 2 μm or more, 2 points: fluctuation range of 1.5 μm or more and less than 2 μm, 3 points: fluctuation range of 1.0 μm or more and less than 1.5 μm, 4 points: fluctuation range of 0.5 μm or more and less than 1.0 μm, 5 points : The fluctuation range is less than 0.5 μm

<Evaluation of rectangularity>
A photosensitive resin composition is applied to a cleaned and HMDS-treated glass substrate with a film thickness of 1.3 μm, exposed and developed through a mask, then post-baked at 140 ° C., and 2.5 μm line and space after post-baking. The rectangularity of the shape of the pattern part was evaluated.
1 point: Dome-shaped cross section with no corners and taper angle of less than 45 ° 2 points: Dome shape with cross-sections with no corners and taper angle of 45 ° to less than 60 ° 3 points: Dome shape with cross-sections and corners Tapering angle of 60 ° or more and less than 75 ° 4 points: Cross section has an angle and taper angle of 60 ° or more but less than 75 ° 5 points: Section shape has an angle and taper angle of 75 ° or more

<Evaluation of remaining film properties>
A point where a photosensitive resin composition was applied to a cleaned and HMDS-treated glass substrate with a film thickness of 1.3 μm, developed without exposure, and evaluated as a residual film by the ratio of the film thickness after development to the film thickness before development. : Remaining film is less than 50% 2 points: Remaining film is 50% or more and less than 70% 3 points: Remaining film is 70% or more and less than 80% 4 points: Remaining film is 80% or more and less than 90% 5 points: Remaining film is 90 %that's all

<Overall performance>
The numerical values of evaluation of sensitivity, resolution, PED, rectangularity, and residual film property were totaled and evaluated as the overall performance according to the following criteria.
1: 17 points or less 2: 18 points or more and 19 points or less 3: 20 points or more and 21 points or less 4: 22 points or more and 23 points or less 5: 24 points or more

  As shown in the above table, the photosensitive resin composition of each example is one of sensitivity, resolution, PED, residual film property and rectangularity in comparison with the photosensitive resin composition of each comparative example. As a result, it was found that excellent results were obtained. Comparative Examples 1 to 3 that do not contain a parahydroxystyrene resin, and Comparative Examples 4 and 7 to 9 in which the polydispersity of the parahydroxystyrene resin is outside the range of 1.5 to 5.0 are sensitivity, PED, and rectangle. It turned out that either evaluation of sex was inferior. Further, it was found that Comparative Examples 5 and 6 containing only one of the A1 component and the A2 component were inferior in sensitivity, resolution, PED, remaining film property, and rectangularity as compared with the Examples. .

(Example 100)
<Organic EL display device>
An organic EL display device having an ITO pattern was produced by the following method (see FIG. 1).
A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. . The wiring 2 is used to connect the TFT 1 with an organic EL element formed between TFTs 1 or in a later process.

Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarizing film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition described in Example 1 of JP-A-2009-98616 on a substrate and pre-baking (90 ° C. × 2 minutes), after irradiating 45 mJ / cm ² (illuminance 20 mW / cm ² ) with i-line (365 nm) using a high-pressure mercury lamp from above the mask, developing with an alkaline aqueous solution to form a pattern at 230 ° C. A heat treatment for 60 minutes was performed.
The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.

Next, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. Thereafter, the photosensitive resin composition of Example 1 was spin-coated on an ITO substrate, pre-baked on a hot plate (90 ° C. × 2 minutes), and then i-line (365 nm) was 20 mJ from above the mask using a high-pressure mercury lamp. After irradiation with / cm ² (illuminance 20 mW / cm ² ), the pattern was formed by developing with an alkaline aqueous solution. Then, the post-baking heat processing for 3 minutes were performed at 140 degreeC before the etching process. Using this resist pattern as a mask, ITO was patterned by wet etching by dipping in an ITO etchant (3% aqueous oxalic acid solution) at 40 ° C./1 min. Thereafter, the resist pattern was peeled off by being immersed in a resist stripping solution (MS2001, manufactured by Fuji Film Electronics Materials Co., Ltd.) at 70 ° C. for 7 minutes. The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

  Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. As the insulating film 8, the photosensitive resin composition described in Example 1 of JP2009-98616A was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.

  Furthermore, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus. Next, a second electrode made of Al was formed on the entire surface above the substrate. The obtained board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.

  As described above, an organic EL display device having an active matrix type ITO pattern formed by connecting each organic EL element to TFT 1 for driving the organic EL element was obtained. When a voltage was applied via the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.

(Example 200)
<Liquid crystal display device>
A liquid crystal display device having an ITO pattern was produced by the following method.
In the active matrix liquid crystal display device described in FIG. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 200 was obtained.
That is, the cured film 17 was formed as an interlayer insulating film by the same method as the method for forming the planarizing film 4 of the organic EL display device in Example 100.

  When a drive voltage was applied to the obtained liquid crystal display device having the ITO pattern, it was found that the liquid crystal display device showed good display characteristics and high reliability.

1: TFT (Thin Film Transistor)
2: Wiring 3: Insulating film 4: Flattened film 5: First electrode 6: Glass substrate 7: Contact hole 8: Insulating film 10: Liquid crystal display device 12: Backlight unit 14, 15: Glass substrate 16: TFT
17: Cured film 18: Contact hole 19: ITO transparent electrode 20: Liquid crystal 22: Color filter

Claims (13)

(A1) a polymer containing a repeating unit (a1) represented by the following general formula (I) and a repeating unit (a2) represented by the following general formula (II):
(A2) a polymer containing a repeating unit (a3) represented by the following general formula (III) and a repeating unit (a2) represented by the following general formula (II):
(B) a parahydroxystyrene resin having a weight average molecular weight of 2000 to 15000 and a polydispersity of 1.5 to 5.0,
(C) a photoacid generator,
A positive photosensitive resin composition comprising (D) a basic compound and (E) a solvent.
(In general formula (I), R ² represents a hydrogen atom or a methyl group, R ³ represents a hydrogen atom, a chain alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or 6 carbon atoms. Represents an aryl group having 10 to 10 carbon atoms or an aralkyl group having 7 to 11 carbon atoms, R ⁴ and R ⁵ are each independently an unsubstituted chain alkyl group having 1 to 10 carbon atoms and an unsubstituted halogen atom having 1 to 10 carbon atoms. A chain alkyl group, an unsubstituted cyclic alkyl group having 3 to 10 carbon atoms, an unsubstituted aryl group having 6 to 10 carbon atoms, or an unsubstituted aralkyl group having 7 to 11 carbon atoms;
In general formula (II), R ¹ represents a hydrogen atom or a methyl group;
In general formula (III), Ra ^{1 to} Ra ⁶ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group. Ra ² and Ra ³ , Ra ⁴ and Ra ⁵ may be bonded to each other to form a ring. Ra ⁷ represents a hydrogen atom or a methyl group, Ra ⁸ represents a halogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms, and n1 represents an integer of 0 to 4. ) The component (A1) is a polymer (A1 ′) having a repeating unit represented by the following general formula (I ′) and a repeating unit represented by the following general formula (II ′):
The component (A2) is a polymer (A2 ′) having a repeating unit represented by the following general formula (III ′) and a repeating unit represented by the following general formula (II ′):
The positive photosensitive resin composition according to claim 1, comprising at least one of the polymer (A1 ′) and the polymer (A2 ′).
(In General Formula (I ′), R ⁶ represents an unsubstituted alkyl group having 1 to ⁶ carbon atoms. In General Formula (III ′), Ra ¹¹ and Ra ¹² are each independently a hydrogen atom or carbon number 1. Represents an alkyl group of ˜6 or a phenyl group, and Ra ¹¹ and Ra ¹² may be bonded to each other to form a 5- to 7-membered ring.) The positive photosensitive resin composition according to claim 1 or 2, wherein the (C) photoacid generator includes an oxime sulfonate structure represented by the following general formula (b1).
(In the general formula (b1), R ¹ represents an alkyl group, a cycloalkyl group, a heteroaryl group, or an aryl group.) The basic compound (D) is represented by the following general formula (Qa), the following general formula (Qb), and the following general formula (Qc). The positive photosensitive resin composition of any one of Claims 1-3 containing at least 1 sort (s) of a compound.
(In General Formula (a), R ² represents an alkyl group which may have a substituent having 1 to 6 carbon atoms or a cycloalkyl group which may have a substituent having 3 to 10 carbon atoms. X represents an oxygen atom or a sulfur atom, Y ¹ represents an oxygen atom or a —NH— group, and p1 represents an integer of 1 to 3.)
(In the general formula (Qb), R ⁸ , R ⁹ and R ¹⁰ each independently have a hydrogen atom, an alkyl group which may have a substituent of 1 to 6 carbon atoms, or a substituent. Represents an aryl group which may be substituted, or a cycloalkyl group which may have a substituent having 3 to 10 carbon atoms.
5. The weight average molecular weight of at least one of the component (A1) and the component (A2) is 2000 to 15000, and the polydispersity is 1.5 to 5.0. 5. The positive photosensitive resin composition as described. The positive photosensitive resin composition according to any one of claims 1 to 5, wherein a content of the component (A2) is 30 to 97% by weight with respect to the entire photosensitive resin composition. The positive photosensitive resin composition according to any one of claims 1 to 6, wherein a weight ratio (A1: A2) of the component (A1) to the component (A2) is 50:50 to 5:95. . The positive photosensitive resin composition according to any one of claims 1 to 7, wherein 95% by weight or more of the polymer component contained in the photosensitive resin composition is composed of a repeating unit derived from hydroxystyrene. (1) A step of applying the positive photosensitive resin composition according to any one of claims 1 to 8 on a substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) a step of exposing with actinic radiation,
(4) a step of developing with an aqueous developer,
(5) a step of etching the substrate using the formed resist pattern as a mask; and
(6) A method for producing a pattern comprising the step of stripping the resist pattern. The manufacturing method of the pattern of Claim 9 including the process of post-baking the said resist pattern at 100-160 degreeC after the said image development process and before an etching process. 11. The substrate according to claim 9, wherein the substrate is an ITO substrate, an IGZO substrate, a molybdenum substrate, a Ti substrate, an Al substrate, a Cu substrate, a tungsten substrate, a silicon oxide substrate, a silicon nitride substrate, or a silicon substrate. Pattern manufacturing method. The manufacturing method of an organic electroluminescence display or a liquid crystal display device containing the manufacturing method of the pattern of any one of Claims 9-11. The cured film formed by hardening | curing the positive photosensitive resin composition of any one of Claims 1-8.