KR101729599B1 - Photosensitive resin composition and production method for pattern using same - Google Patents

Abstract

The present invention provides a photosensitive resin composition excellent in sensitivity, line width stability, resolution and rectangularity. (A1) a polymer component comprising a polymer having a structural unit (a1) represented by the following general formula (1), (B) a photoacid generator, (C) an alicyclic epoxy compound, and (D1) Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ¹ and R ² represents an alkyl group Or an aryl group; R ³ represents an alkyl group or an aryl group, R ¹ or R ² and R ³ may be connected to form a cyclic ether; R ⁴ represents a hydrogen atom or a methyl group]

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition,

The present invention relates to a photosensitive resin composition and a method for producing a pattern using the same. The present invention also relates to a method of manufacturing an organic EL display device or a liquid crystal display device including such a pattern manufacturing method, and a pattern produced by the pattern manufacturing method. More specifically, the present invention relates to a positive photosensitive resin composition suitable for forming resist etching of electronic components such as a liquid crystal display device, an organic EL display device and the like, and a method of producing a pattern using the positive photosensitive resin composition.

In organic EL display devices, liquid crystal display devices, and the like, metal wiring patterns such as patterned ITO films are provided. For pattern formation of the ITO film or the like, it is widely known to apply a photosensitive resin composition on an ITO film, remove the solvent, expose and develop it, and etch the ITO film using the formed pattern as a mask.

In addition, in recent years, high resolution of ITO processing has been required in order to make display characteristics of an organic EL display device and a liquid crystal display device high-definition. In order to finely process ITO with high definition, high resolution of a photosensitive resin composition which functions as a mask at the time of etching is required. For this reason, a photosensitive resin composition capable of obtaining a fine pattern shape with high definition has been studied (for example, Patent Document 1, Patent Document 2, etc.).

Japanese Patent Laid-Open No. 9-325473 Japanese Patent Laid-Open No. 10-326015

However, according to recent technology development, a further improved photosensitive resin composition is required for sensitivity, line width stability, resolution and rectangularity. The object of the present invention is to solve such a demand, and it is an object of the present invention to provide a further improved photosensitive resin composition with respect to sensitivity, line width stability, resolution and rectangularity.

Under such circumstances, the inventors of the present invention have conducted intensive studies, and as a result, found that the inclusion of a predetermined polymer, an alicyclic epoxy compound, and a predetermined solvent improves sensitivity, line width stability, resolution and rectangularity, It came to the following.

Specifically, the above problems are solved by the following means <1>, preferably by <2> - <13>.

<1> (A1) A polymer composition comprising a polymer having a structural unit (a1) represented by the following general formula (1)

(B) a photoacid generator,

(C) an alicyclic epoxy compound, and

(D1) A photosensitive resin composition comprising a solvent containing two or more acetate structures in a molecule.

[In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ¹ and R ² is an alkyl group or an aryl group; R ³ represents an alkyl group or an aryl group, R ¹ or R ² and R ³ may be connected to form a cyclic ether; R ⁴ represents a hydrogen atom or a methyl group]

<2> The photosensitive resin composition according to <1>, wherein the (C) alicyclic epoxy compound is a compound represented by the following general formula (I).

[In the general formula (I), n represents an integer of 1 to 4; R ¹ represents an organic group having 1 to 15 carbon atoms]

&Lt; 3 > The photosensitive resin composition according to < 2 >, wherein n in the compound represented by the general formula (I) is 1 or 2. [

(4) The photosensitive resin composition according to any one of (1) to (3), further comprising (A2) a polymer component having a structural unit (a4) having a protected carboxyl group protected with an acid-decomposable group.

<5> The photosensitive resin composition according to <4>, wherein the structural unit (a4) is a structural unit represented by the following general formula (A2 ').

Wherein at least one of R ¹ and R ² is an alkyl group or an aryl group, R ³ is an alkyl group or an aryl group, and R ¹ and R ² are each independently a hydrogen atom, an alkyl group or an aryl group, , R ¹ or R ² and R ³ may be connected to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or an arylene group,

<6> The photosensitive resin composition according to any one of <1> to <5>, wherein the content of the (C) alicyclic epoxy compound is 0.05 to 5% by mass based on the total solid content.

&Lt; 7 > A liquid crystal display according to any one of < 1 > to < 6 >, wherein the solvent contains two or more acetate structures in the molecule (D1) (D2). &Lt; / RTI &gt;

<8> A photosensitive resin composition according to any one of <1> to <7>, wherein the solvent having two or more acetate structures in the molecule (D1) has a boiling point of 130 ° C. or more and less than 300 ° C.

<9> The photosensitive resin composition according to any one of <1> to <8>, wherein the content of the solvent containing two or more acetate structures in the molecule (D1) is 1 to 10% Resin composition.

(1) a step of applying a photosensitive resin composition described in any one of <1> to <9> on at least one surface of a substrate,

(2) a step of forming a photosensitive resin composition layer by volatilizing the organic solvent by drying,

(3) a step of exposing the photosensitive resin composition layer,

(4) a step of developing the exposed photosensitive resin composition layer.

<11> The method for producing a pattern according to <10>, which comprises a step of performing etching using a formed pattern as an etching resist, and a step of removing the pattern by a plasma treatment or a chemical treatment.

<12> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <9>.

&Lt; 13 > An organic EL display device or a method of manufacturing a liquid crystal display device, which comprises the method of producing a pattern according to < 10 >

(Effects of the Invention)

According to the present invention, it becomes possible to provide a photosensitive resin composition having high sensitivity, excellent line width stability, resolution and rectangularity.

Fig. 1 shows a configuration diagram of an example of an organic EL display device. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and has a planarizing film 4.
2 is a conceptual diagram showing an example of the configuration of a liquid crystal display device. 1 is a schematic sectional view of an active matrix substrate in a liquid crystal display device and has a cured film 17 as an interlayer insulating film.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, &quot; &quot; is used to mean that the numerical values described before and after the lower limit and the upper limit are included. The organic EL display device in the present invention refers to an organic electroluminescence display device. The polydispersity in the present invention refers to the value of Mw / Mn.

In the notation of the group (atomic group) in the present specification, the notation which does not include substitution and non-substitution includes not only a substituent but also a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

Further, (meth) acrylic acid means acrylic acid and / or methacrylic acid.

The photosensitive resin composition of the present invention (hereinafter sometimes referred to as &quot; the composition of the present invention &

(A1) a polymer component comprising a polymer having a structural unit (a1) represented by the following general formula (1)

(B) a photoacid generator,

(C) an alicyclic epoxy compound, and

(D1) a solvent containing two or more acetate structures in the molecule.

[In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ¹ and R ² is an alkyl group or an aryl group; R ³ represents an alkyl group or an aryl group, R ¹ or R ² and R ³ may be connected to form a cyclic ether; R ⁴ represents a hydrogen atom or a methyl group]

The photosensitive resin composition of the present invention is preferably used as a chemically amplified positive photosensitive resin composition.

Hereinafter, the composition of the present invention will be described in detail.

<Polymer Component>

The photosensitive resin composition of the present invention comprises, as the polymer component (A), (A1) a polymer component having a structural unit (a1) represented by the following general formula (1) (A1) The polymer component may contain a polymer other than the structural unit (a1) represented by the general formula (1). It is also preferable that the polymer component (A2) has the structural unit (a4) having a protected carboxyl group protected with an acid-decomposable group.

Hereinafter, these polymer components will be described.

&Lt; Polymer component (A1) &gt;

The polymer component (A1) in the present invention is a polymer component comprising a polymer having the structural unit (a1) represented by the general formula (1). (A1) has the structural unit (a1), a photosensitive resin composition excellent in resolution and rectangularity can be obtained.

[In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ¹ and R ² is an alkyl group or an aryl group; R ³ represents an alkyl group or an aryl group, R ¹ or R ² and R ³ may be connected to form a cyclic ether; R ⁴ represents a hydrogen atom or a methyl group]

R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ¹ and R ² is an alkyl group or an aryl group.

The alkyl group is preferably an alkyl group having from 1 to 10 carbon atoms, more preferably an alkyl group having from 1 to 8 carbon atoms, and still more preferably an alkyl group having from 1 to 6 carbon atoms. The alkyl group may have a substituent. The alkyl group may be any of linear, branched and cyclic, but a linear alkyl group is preferred. Examples of the alkyl group include methyl, ethyl, propyl, butyl, t-butyl, pentyl, hexyl and cyclohexyl.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms. The aryl group may have a substituent. As the aryl group, for example, a phenyl group, a naphthyl group, and an anthracenyl group are exemplified.

Examples of the substituent which the alkyl group and the aryl group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a thioalkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a cyano group, a halogen atom (fluorine atom, Atom, iodine atom), and the like. These substituents may further have a substituent.

Among them, R ¹ and R ² are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and particularly preferably one of R ¹ and R ² is a methyl group and the other is a hydrogen atom.

R ³ represents an alkyl group or an aryl group. The alkyl group and aryl group represented by R ³ are the same as the alkyl group and aryl group in R ¹ and R ² . R ³ is preferably a methyl group, an ethyl group or a propyl group, more preferably an ethyl group or a propyl group.

R ³ may be linked with R ¹ or R ² to form a cyclic ether. The cyclic ether formed by linking with R ¹ or R ² is preferably a cyclic ether of 3 to 6 membered ring, more preferably a cyclic ether of 5 to 6 membered ring.

Specific examples of the structural unit (a1) represented by the general formula (1) include the following structures, but the present invention is not limited to the following structures.

From the viewpoint of high sensitivity, it is preferable that the polymer component (A1) contains a polymer having the structural unit (a2) represented by the following general formula (2) in addition to the structural unit (a1).

[In the general formula (2), R ⁴ is a hydrogen atom or a methyl group]

R ⁴ is preferably a hydrogen atom.

The OH group may be any of p-, m-, and o-, but is preferably bonded to the p-position.

The constituent unit represented by the general formula (2) is preferably from 5.0 to 30 mol%, more preferably from 10 to 20 mol%, of the constituent units of the (A1) polymer component. If the amount is smaller than the above range, the effect can not be obtained. If the amount is too large, the sensitivity becomes high and the exposure process margin becomes narrow.

Among the constituent units constituting the polymer (A1), the constituent unit represented by the general formula (1) is preferably from 5 to 40 mol%, more preferably from 10 to 40 mol%, of the constituent units of the (A1) And more preferably 20 to 35 mol%.

The protection ratio of the (A1) polymer is preferably 1 to 60%, more preferably 5 to 50%, and still more preferably 10 to 40%. By setting this range, image discoloration, sensitivity, and resolution are improved. The protection ratio refers to (A1) the molar ratio of the protected groups in which 100 mol% of all the constituent units in the polymer are contained.

The weight average molecular weight (Mw) of the (A1) polymer is preferably in the range of 2000 to 15000, more preferably in the range of 5000 to 12000, and still more preferably in the range of 7,500 to 12,000. 2000 or more, an effect that the formed pixel can maintain the rectangularity even after heating by post-baking is obtained, and when it is 15000 or less, the effect of improving the sensitivity and the PED characteristic can be obtained. Here, the weight average molecular weight is defined by a polystyrene conversion value of the gel permeation chromatography.

The polydispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the (A1) polymer is preferably 1.0 to 4.0, more preferably 1.5 to 3.5, and still more preferably 2.0 to 3.0. By setting this range, the rectangularity is improved.

&Lt; Polymer component (A2) &gt;

The photosensitive resin composition of the present invention may contain a polymer component (A2) in addition to the polymer component (A1). (A2) a polymer component having a structural unit (a4) having a protected carboxyl group protected with an acid-decomposable group is preferable. Herein, the acid-decomposable group means a functional group capable of decomposing in the presence of an acid.

The polymer component in the composition of the present invention is preferably alkali-insoluble and is preferably a resin that becomes alkali-soluble when the acid-decomposable group of the structural unit represented by the general formula (A2 ') is decomposed. The constitutional unit having a protected carboxyl group in which the carboxyl group is protected by an acid-decomposable group decomposes the protecting group by an acid, so that a carboxyl group can be produced. Here, in the present invention, the term "alkali solubility" means that the solution of the compound (resin) is coated on a substrate and heated at 23 ° C. to a coating film (thickness 3 μm) of the compound (resin) formed by heating at 90 ° C. for 2 minutes Refers to a dissolution rate in a 0.4% aqueous solution of tetramethylammonium hydroxide in a solution of the compound (resin) in an aqueous solution of 0.01 m / sec or more. The term "alkali insoluble" means that the solution of the compound Means that the dissolution rate of the coating film (thickness 3 占 퐉) of the compound (resin) to be formed in an aqueous solution of 0.4% tetramethylammonium hydroxide at 23 占 폚 is less than 0.01 占 퐉 / second.

Examples of the constituent unit having a protected carboxyl group protected by an acid-decomposable group include a constitutional unit having a protected carboxyl group protected by an acid-decomposable group described in paragraphs [0021] to [0055] of Japanese Patent Application Laid- A structural unit having a protected carboxyl group protected by an acid-decomposable group described in paragraphs [0020] to [0052] of the gazette is exemplified, and the contents thereof are included in this specification. Among them, the polymer component (A2) is preferably a polymer component having a structural unit (a4) in which the acid group of the structure represented by the following general formula (A2 ') has a group protected with an acid decomposable group. The acidic group in the present invention means a proton dissociable group having a pKa smaller than 7. The acid group is usually incorporated into the polymer as a constituent unit containing an acid group by using a monomer capable of forming an acid group. Including such a structural unit containing an acid group in the polymer tends to be easily dissolved in an alkaline developer. The component (A2) has the structural unit (a4), whereby a highly sensitive photosensitive resin composition can be obtained.

Wherein at least one of R ¹ and R ² is an alkyl group or an aryl group, R ³ is an alkyl group or an aryl group, and R ¹ and R ² are each independently a hydrogen atom, an alkyl group or an aryl group, , R ¹ or R ² and R ³ may be connected to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or an arylene group,

When R ¹ and R ² are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferable. When R ¹ and R ² are aryl groups, a phenyl group is preferred. R ¹ and R ² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

R ³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 6 alkyl groups.

X ⁰ represents a single bond or an arylene group, and a single bond is preferable.

Preferable specific examples of the structural unit represented by the general formula (A2 ') include the following structural units. R represents a hydrogen atom or a methyl group.

The structural unit represented by the general formula (A2 ') is preferably from 10 to 80 mol%, more preferably from 20 to 80 mol%, and still more preferably from 30 to 70 mol% of the constituent units of the (A2) polymer component.

The content of the other structural units in the structural unit constituting the polymer component (A2) is preferably 60 mol% or less, more preferably 50 mol% or less, and still more preferably 40 mol% or less. The lower limit may be 0 mol%, for example, 1 mol% or more and 5 mol% or more. Within the range of the above-mentioned numerical values, various properties of the cured film obtained from the photosensitive resin composition are improved.

The protection ratio of the polymer component (A2) is preferably 1 to 60%, more preferably 5 to 50%, and still more preferably 10 to 40%. By setting this range, the sensitivity is improved and the discrimination between the solubility of the exposed portion and the unexposed portion is improved. The protection ratio refers to the molar ratio of the protected group (A2) in which 100 mol% of all the structural units in the polymer component are contained.

The weight average molecular weight (Mw) of the polymer component (A2) is preferably in the range of 2,000 to 15,000, more preferably 5,000 to 12,000, and still more preferably 7,500 to 12,000. 2000 or more, an effect that the formed pixel can maintain the rectangularity even after heating by post-baking is obtained, and when it is 15000 or less, the effect of improving the sensitivity and the PED characteristic can be obtained. Here, the weight average molecular weight is defined by a polystyrene conversion value of the gel permeation chromatography.

The polydispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polymer component (A2) is preferably 1.0 to 4.0, more preferably 1.5 to 3.5, still more preferably 2.0 to 3.0. By setting this range, the rectangularity is excellent.

- mixing ratio of component (A1) to component (A2)

The photosensitive resin composition of the present invention preferably contains (A1) and (A2) as a polymer component. These mass ratios are preferably 1: 6 to 6: 1, more preferably 2: 5 to 8: 1. By setting this range, the effect of the present invention tends to be exerted more effectively.

<< Polymer Component >>

In the present invention, the component (A) may contain, in addition to the above structural units (a1), (a2) and (a4), the other structural unit (a3). These constituent units may include either or both of the polymer components (A1) and (A2). Unlike the polymer component (A1) or (A2), a polymer component (A3) having another structural unit (a3) which does not substantially contain (a1), (a2) and (a4) may be contained. (A3) other than (a1), (a2) and (a4) different from the polymer component (A1) or (A2), the amount of the polymer component Is preferably 60 mass% or less, more preferably 40 mass% or less, and even more preferably 20 mass% or less, of the total polymer components.

The structural unit (monomer) composed of the other structural unit (a3) is not particularly limited, and examples thereof include styrene, alkyl (meth) acrylate, cyclic alkyl (meth) acrylate, aryl (meth) acrylate, An unsaturated aromatic compound, a conjugated diene compound, an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated dicarboxylic acid anhydride, and other unsaturated compounds can be used as the aromatic dicarboxylic acid diester, the dicarboxylic acid diester, the bicyclic unsaturated compounds, the maleimide compounds, have. Further, as described later, it may have a structural unit having an acidic group. Monomers comprising other structural unit (a3) may be used alone or in combination of two or more.

The composition of the present invention preferably contains the polymer component in a proportion of at least 60% by weight based on the total solid content of the composition, more preferably at least 80% by weight.

The proportion of the constituent unit having a pKa of 9 or more out of the whole polymer components in the composition of the present invention is preferably 10 to 80 mol%, more preferably 20 to 70 mol%. The proportion of the constituent unit having a pKa of 5 or less in the total polymer components in the composition of the present invention is preferably 0 to 20 mol%, more preferably 5 to 10 mol%. By incorporating a small amount of weak acid structural units, even when a relatively strong alkaline developer (for example, exceeding 2.38% TMAH aqueous solution pH 13) is used for development, the polymer hardly swells in the developer and does not undergo film- Can be developed. As a result, the pattern to be formed becomes better. Further, since the content of the constituent unit of the strong acid is 20% or less, pattern formation with higher sensitivity becomes possible.

&Lt; (B) Photo acid generator >

The photosensitive resin composition of the present invention contains (B) a photoacid generator. As the photoacid generator (referred to as &quot; component (B) &quot;) used in the present invention, a compound which generates an acid upon exposure to an actinic ray having a wavelength of 300 nm or longer, preferably 300-450 nm is preferable, It is not. Also, with respect to a photoacid generator which does not directly react with an actinic ray having a wavelength of 300 nm or more, a compound capable of generating an acid in response to an actinic ray having a wavelength of 300 nm or more by using in combination with a sensitizer can be preferably used in combination with a sensitizer. As the photoacid generator used in the present invention, a photoacid generator that generates an acid with a pKa of 4 or less is preferable, a photoacid generator that generates an acid with a pKa of 3 or less is more preferable, and a photoacid generator that generates an acid with 2 or less is the most preferable Do.

Examples of the photoacid generator include trichloromethyl-s-triazine, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imidosulfonate compounds and oxime sulfonate compounds. Among them, it is preferable to use an oxime sulfonate compound from the standpoint of insulation. These photoacid generators may be used alone or in combination of two or more. Specific examples of trichloromethyl-s-triazine, diaryl iodonium salts, triarylsulfonium salts, quaternary ammonium salts and diazomethane derivatives are disclosed in JP-A No. 2011-221494, paragraphs [0083] to [ 0088] can be exemplified.

As the oxime sulfonate compound, that is, the compound having an oxime sulfonate structure, a compound containing an oxime sulfonate structure represented by the following general formula (B1) can be preferably exemplified.

In general formula (B1)

[In the formula (B1), R ²¹ represents an alkyl group or an aryl group. The dashed line indicates the combination with other tiles.

The alkyl group in R &lt; ²¹ &gt; may be linear, branched or cyclic. The permissible substituents are described below.

As the alkyl group for R ²¹ , a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group of R ²¹ includes an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or a cycloalkyl group (including bridged alicyclic groups such as 7,7-dimethyl-2-oxononorbornyl group, Preferably a bicycloalkyl group or the like).

As the aryl group for R ^21, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ²¹ may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.

It is also preferable that the compound containing an oxime sulfonate structure represented by the general formula (B1) is an oxime sulfonate compound represented by the following general formula (B2).

Wherein (B2) in, R ⁴² is an alkyl group or aryl group, X is an alkyl group, an alkoxy group, or a halogen atom, m4 is an integer of 0 to 3, a plurality of X when m4 is 2 or 3 is Same or different]

The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

As the X, the alkoxy group is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.

The halogen atom as X is preferably a chlorine atom or a fluorine atom. m4 is preferably 0 or 1. In the above general formula (B2), and m4 are 1, X is a methyl group, the substitution position of X is the ortho position, R ⁴² is 1 to 10 carbon atoms of straight chain alkyl, 7,7-dimethyl-2-oxo-norbornyl A n-methyl group or a p-toluyl group is particularly preferable.

It is also preferable that the compound containing an oxime sulfonate structure represented by the above general formula (B1) is an oxime sulfonate compound represented by the following general formula (B3).

Wherein R ⁴³ is the same as R ⁴² in the formula (B2), X ¹ is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, And n4 represents an integer of 0 to 5,

Examples of R ⁴³ in the general formula (B3) include methyl, ethyl, n-propyl, n-butyl, n-octyl, A perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferable, and an n-octyl group is particularly preferable.

X ¹ is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group.

n4 is preferably 0 to 2, and particularly preferably 0 to 1.

Specific examples of the compound represented by the general formula (B3) include? - (methylsulfonyloxyimino) benzyl cyanide,? - (ethylsulfonyloxyimino) benzyl cyanide,? - (n-propylsulfonyloxyimino) Benzyl cyanide,? - (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, n-butylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, and? - [(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile.

Specific examples of the preferable oxime sulfonate compound include the following compounds (i) to (viii), and they may be used singly or in combination of two or more. The compounds (i) to (viii) are commercially available. It may also be used in combination with other types of photo acid generators (B).

The compound containing an oxime sulfonate structure represented by the above 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 a heteroaryl group . R ¹⁰² represents an alkyl group or an aryl group.

¹⁰¹ X is ^{-O-, -S-, -NH-, -NR 105} -, -CH 2 -, -CR 106 H- or -CR ¹⁰⁵ R ¹⁰⁷ - represents a, R ¹⁰⁵ ~R ¹⁰⁷ is an alkyl group or an aryl group .

R ¹²¹ to R ¹²⁴ independently represent 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. 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 at least two of R ¹²¹ to R ¹²⁴ are bonded to each other to form an aryl group. Among them, a form in which all of R ¹²¹ to R ¹²⁴ are hydrogen atoms is preferable from the viewpoint of sensitivity.

All of the functional groups described above may further have a substituent.

The compound represented by the above 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 and R ¹²¹ to R ¹²⁴ are the same as those in the formula (OS-1), and preferred examples are also the same.

Of these, R ^{101 in} the general formulas (OS-1) and (OS-2) is preferably a cyano group or an aryl group, more preferably a form represented by the general formula (OS-2) ¹⁰¹ is a cyano group, a phenyl group or a naphthyl group is most preferable.

Further, in the oxime sulfonate compound, the stereostructure (E, Z, etc.) of oxime or benzothiazole ring may be either one or both of them.

Specific examples of the compounds represented by the above general formula (OS-1) which can be suitably used in the present invention include compounds (exemplified compounds b-1 to b-1) described in paragraphs [0128] to [0132] To b-34), but the present invention is not limited to these.

In the present invention, the compound having an oxime sulfonate structure represented by the general formula (B1) is represented by the following general formula (OS-3), the following general formula (OS-4) It is preferable that the luminescent oxime sulfonate compound is a luminescent oxime sulfonate compound.

In the formulas (OS-3) to (OS-5), R ²² , R ²⁵ and R ²⁸ each independently represent an alkyl group, an aryl group or a heteroaryl group, and R ²³ , R ²⁶ and R ²⁹ each represent An alkyl group, an aryl group or a halogen atom; 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 represent an integer of 0 to 6,

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.

Of the above-mentioned formulas (OS-3) to (OS-5), the alkyl group for R ²² , R ²⁵ and R ²⁸ is preferably an alkyl group having 1 to 30 total carbon atoms which may have a substituent.

Of the above general formulas (OS-3) to (OS-5), the aryl group for R ²² , R ²⁵ and R ²⁸ is preferably an aryl group having 6 to 30 total carbon atoms which may have a substituent.

Of the above general formulas (OS-3) to (OS-5), the heteroaryl group for R ¹ is preferably a heteroaryl group having 4 to 30 total carbon atoms which may have a substituent.

Of the above-mentioned general formulas (OS-3) to (OS-5), the heteroaryl group in R ²² , R ²⁵ and R ²⁸ may be at least one of the rings is a heteroaromatic ring, and examples thereof include a heteroaromatic ring and a benzene ring There may be.

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, more preferably a hydrogen atom or an alkyl group.

Of the above general formulas (OS-3) to (OS-5), one or two of R ²³ , R ²⁶ and R ²⁹ in which at least two of R ²³ , R ²⁶ and R ²⁹ are present in the compound are preferably an alkyl group, More preferably an alkyl group, an aryl group or a halogen atom, and it is particularly preferable that one is an alkyl group and the remainder is a hydrogen atom.

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

The aryl group for R ²³ , R ²⁶ and R ²⁹ is preferably an aryl group having 6 to 30 total 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 reduction 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 When X ^{1 to} X ³ are S, it is preferable that n ^{1 to} n ³ are each independently 2.

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. Among them, it is preferable that R ²⁴ , R ²⁷ and R ³⁰ are 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.

Among the above-mentioned general formulas (OS-3) to (OS-5), the alkyl group for R ²⁴ , R ²⁷ and R ³⁰ is preferably an alkyl group having 1 to 30 total carbon atoms which may have a substituent.

Of the above general formulas (OS-3) to (OS-5), the alkyloxy group for R ²⁴ , R ²⁷ and R ³⁰ is preferably an alkyloxy group having 1 to 30 total carbon atoms which may have a substituent.

In the formulas (OS-3) to (OS-5), m ^{1 to} m ³ each independently represent an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1 , And particularly preferably 0.

(OS-3) to (OS-5) described in paragraphs [0092] to [0109] of JP-A No. 2011-221494, The preferable range of the substituent of 5) is also preferable.

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

Equation (OS-6) ~ (OS -11) of, R ³⁰¹ ~R ³⁰⁶ represents an alkyl group, an aryl group or a heteroaryl group, R ³⁰⁷ represents a hydrogen atom or a bromine atom, R ³⁰⁸ ~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 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,

(OS-6) to (OS-11) described in paragraphs [0110] to [0112] of JP-A No. 2011-221494 ). &Lt; / RTI &gt;

Specific examples of the oxime sulfonate compound represented by the above general formulas (OS-3) to (OS-5) include compounds described in paragraphs [0114] to [0120] of Japanese Patent Laid- However, the present invention is not limited to these.

In the photosensitive resin composition of the present invention, the photoacid generator (B) is used in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the total resin component (preferably the solid content, more preferably the total amount of the copolymer) in the photosensitive resin composition More preferably 0.5 to 10 parts by mass. Two or more species may be used in combination.

<(C) Alicyclic epoxy compound>

The photosensitive resin composition of the present invention contains an alicyclic epoxy compound as a crosslinking agent. It is considered that the alicyclic epoxy compound is a photosensitive resin composition which is excellent in sensitivity, line width stability, resolution and rectangularity by incorporating such a compound in order to quickly trap an acid by an acid generator.

The alicyclic epoxy group contained in the alicyclic epoxy compound used in the present invention is not particularly limited, and examples thereof include alicyclic epoxy groups directly added to cyclic aliphatic hydrocarbons, and cyclic aliphatic hydrocarbons are preferably 3 to 10 member rings, And a 5- to 6-membered ring is more preferable. Among them, the alicyclic epoxy group is preferably the following alicyclic epoxy group.

The alicyclic epoxy compound is preferably represented by the following formula (I).

[In the formula (I), n represents an integer of 1 to 4; R ¹ represents an organic group having 1 to 15 carbon atoms]

R ¹ represents an organic group having 1 to 15 carbon atoms, which may be branched or unsaturated, and may have a cyclic structure of an aliphatic or aromatic ring. These groups may have oxygen, sulfur, nitrogen, phosphorus, boron, or halogen atoms. The substituent may have a substituent, or the substituents may bond to each other. Also, R ¹ is an n-valent linking group.

The number of carbon atoms of the organic group represented by R ¹ is preferably 1 to 8, and more preferably 1 to 6. The organic group is a hydrocarbon group or a group formed by combining at least one of a hydrocarbon group and a silyl group, -O-, -CO-, -S- and -NR- (R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms) And a group formed by combining a hydrocarbon group or a hydrocarbon group with -O- and / or -CO- is more preferable. The hydrocarbon group is preferably a straight chain or branched group, and more preferably a straight chain group. The number of carbon atoms of the hydrocarbon group is preferably 1 to 4. Two or more hydrocarbon groups may be contained in one organic group.

When the epoxy group in the alicyclic epoxy compound is opened, an epoxy group opened when an acid is generated by the acid generator may bond with a functional group or the like of the polymer, and the degree of freedom of the alicyclic epoxy compound may be lost. Therefore, it is preferable that the number of epoxy groups is small. n represents an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 1 or 2.

As a preferable form of the alicyclic epoxy compound, a compound represented by the following formula (II) is exemplified.

[In the formula (II), R ² represents an organic group having 1 to 15 carbon atoms]

R ² represents an organic group having 1 to 15 carbon atoms, which may be branched or unsaturated, and may have a cyclic structure of an aliphatic or aromatic ring. These groups may have oxygen, sulfur, nitrogen, phosphorus, boron, or halogen atoms. The substituent may have a substituent, or the substituents may bond to each other. Also, R ² is a divalent linking group.

The number of carbon atoms of the organic group of R ² is preferably 1 to 8, and more preferably 1 to 6. The organic group is preferably a hydrocarbon group or a group formed by combining at least one of a hydrocarbon group and -O-, -CO-, -S- and -NR- (R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms) A group formed by combining a hydrocarbon group or a hydrocarbon group with -O- and / or -CO- is more preferable. The hydrocarbon group is preferably a straight chain or branched group, and more preferably a straight chain group. The number of carbon atoms of the hydrocarbon group is preferably 1 to 4. Two or more hydrocarbon groups may be contained in one organic group. The hydrocarbon group is preferably an alkylene group.

The preferred form of the alicyclic epoxy compound is also a compound represented by the following formula (III).

[In the formula (III), R ³ represents an organic group having 1 to 15 carbon atoms]

R ³ represents an organic group having 1 to 15 carbon atoms, which may be branched or unsaturated, and may have a cyclic structure of an aliphatic or aromatic ring. These groups may have oxygen, sulfur, nitrogen, phosphorus, boron, or halogen atoms. The substituent may have a substituent, or the substituents may bond to each other. R ³ is a divalent linking group.

The number of carbon atoms of the organic group of R ³ is preferably 1 to 8, more preferably 1 to 6. The organic group is preferably a hydrocarbon group or a group formed by combining at least one of a hydrocarbon group and -O-, -CO-, -S- and -NR- (R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms) A group formed by combining a hydrocarbon group or a hydrocarbon group with -O- and / or -CO- is more preferable. The hydrocarbon group is preferably a straight chain or branched group, and more preferably a straight chain group. The number of carbon atoms of the hydrocarbon group is preferably 1 to 4. Two or more hydrocarbon groups may be contained in one organic group. The hydrocarbon group is preferably an alkylene group.

Specific examples of the above formulas (I) to (III) include the following compounds, but the present invention is not particularly limited thereto.

The alicyclic epoxy compound to be used in the present invention is not particularly limited, and examples thereof include Maruzen KK Publishing, 4th edition, Experimental Chemistry Lecture 20 Organic Synthesis II, 213 ~, 1992 Alfred Hasfner, The chemistry of heterocyclic compounds-Small Yoshimura, Adhesion, 29, No. 12, 32, 1985, Yoshimura, Adhesion, Vol. 30, No. 5, 42, 1986, Yoshimura, Adhesion, 30, No. 7, 42, 1986, Japanese Patent Publication No. 1-100378, Japanese Patent No. 2906245, and Japanese Patent No. 2926262, which are incorporated herein by reference.

The molecular weight of the alicyclic epoxy compound used in the present invention is preferably less than 1000, and less than 500. By setting this range, the effect of the present invention tends to be exerted more effectively. The lower limit value is not particularly specified, but is usually 100 or more.

The amount of the alicyclic epoxy compound to be added in the photosensitive resin composition of the present invention is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, more preferably 0.1 to 1.5 parts by mass based on 100 parts by mass of the total solid content of the photosensitive resin composition It is more desirable to be negative. The plural alicyclic epoxy compounds may be used in combination, and in that case, the content of the alicyclic epoxy compounds is totaled.

&Lt; (D) Solvent >

The photosensitive resin composition of the present invention (D) contains, as a solvent, a solvent containing two or more acetate structures in the molecule (D1). Although the mechanism is not clear, by improving the sensitivity, line width stability, resolution, and rectangularity, it is possible to improve the sensitivity, line width stability, resolution and rectangularity by promoting proper capture of acid by quencher and alicyclic epoxy compound It is presumed that it becomes possible. The photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential component of the present invention and any of the components described below are dissolved in the (D1) solvent.

(D1) The solvent containing two or more acetate structures in the molecule is not particularly limited as long as it contains two or more acetate structures in the molecule, but the number of acetate structures in the molecule is preferably 2 to 4, more preferably 2 .

The solvent having two or more acetate structures in the molecule (D1) is preferably a solvent having a boiling point of 130 占 폚 or more and less than 300 占 폚, more preferably 180 占 폚 or more and less than 270 占 폚, more preferably 200 占 폚 or more and less than 270 占 폚 Do. The boiling point is the boiling point at 1 atm unless otherwise noted. In the case of a solvent mixture containing two or more solvents, the boiling point is a weighted average of the boiling points of the respective solvents with respect to the total solvent by weight ratios.

(D1) As the solvent, for example, 1,2-ethylene diol diacetate, 1,2-propanediol diacetate, 1,3-propanediol diacetate, 1,2-butanediol diacetate, Acetate, 1,4-butanediol diacetate, 1,6-hexanediol diacetate, triacetin, and the like. (D1) The solvents may be used alone or in combination of two or more.

The content of the (D1) solvent in the photosensitive resin composition of the present invention is preferably 1 to 10% by mass, more preferably 1 to 5% by mass, per 100 parts by mass of the photosensitive resin composition.

Further, another solvent (D2) may be further added to the solvent (D1) to prepare a mixed solvent. In the case of the mixed solvent, other solvent may be selected so that the weighted average of the boiling points of the respective solvents with respect to the total solvent is 130 ° C. or more and less than 300 ° C. (D2). (D2) Other solvents may be used alone or in combination of two or more.

(D2) The other solvent is preferably a solvent having a boiling point of 130 DEG C or more and less than 160 DEG C and a solvent having a boiling point of 160 DEG C or more. Specifically, propylene glycol monomethyl ether acetate (boiling point 146 DEG C), propylene glycol monoethyl ether acetate Lt; 0 &gt; C), and the like; Propyleneglycol methyl-n-butyl ether (boiling point 155 캜), and propylene glycol methyl-n-propyl ether (boiling point 131 캜).

As the solvent having a boiling point of 160 캜 or more, ethyl 3-ethoxypropionate (boiling point: 170 캜), diethylene glycol methyl ethyl ether (boiling point: 176 캜), propylene glycol monomethyl ether propionate (boiling point: 160 캜), dipropylene glycol methyl ether acetate (Boiling point 213 占 폚), 3-methoxybutyl ether acetate (boiling point 171 占 폚), diethylene glycol diethyl ether (boiling point 189 占 폚), diethylene glycol dimethyl ether (boiling point 162 占 폚), diethylene glycol monoethyl ether acetate A boiling point of 220 占 폚), and dipropylene glycol dimethyl ether (boiling point of 175 占 폚).

In addition to the above-mentioned other solvents, known solvents may be used, and 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 monoalkyl ether acetates, esters Ketones, amides, lactones, and the like. Specific examples of the solvent (D2) used in the photosensitive resin composition of the present invention include the solvents described in paragraphs [0174] to [0178] of JP-A No. 2011-221494, the contents of which are incorporated herein by reference .

Further, if necessary, it may be further added with an organic solvent such as benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, A solvent such as 1-nonyl, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate and propylene carbonate may be added. These solvents may be used alone or in combination of two or more. The solvent which can be used in the present invention is preferably used alone or in combination of two or more, more preferably two kinds of solvents, more preferably propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates and diethylene It is more preferable to use the glycol dialkyl ethers or the esters in combination with the butylene glycol alkyl ether acetates.

The content of the solvent (D2) in the photosensitive resin composition of the present invention is preferably 70 to 95 mass%, more preferably 80 to 90 mass%, per 100 mass parts of the photosensitive resin composition.

<Other ingredients>

The photosensitive resin composition of the present invention may further comprise (E) an alkoxysilane compound, (F) a crosslinking agent, (G) a sensitizer, (H) a basic compound, (I) An inhibitor may be preferably added. The photosensitive resin composition of the present invention may contain known additives such as an acid generator, a development accelerator, a plasticizer, a heat radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor.

(E) alkoxysilane compound

The photosensitive resin composition of the present invention is characterized by containing (E) an alkoxysilane compound (referred to as &quot; component (E) &quot;). When the alkoxysilane compound is used, the adhesion between the film formed by the photosensitive resin composition of the present invention and the substrate can be improved, or the properties of the film formed by the photosensitive resin composition of the present invention can be adjusted. As the alkoxysilane compound, a dialkoxysilane compound or a trialkoxysilane compound is preferable, and a trialkoxysilane compound is more preferable. The alkoxy group of the alkoxysilane compound preferably has 1 to 5 carbon atoms.

The (E) alkoxysilane compound that can be used in the photosensitive resin composition of the present invention is an alkoxysilane compound that can be used as an inorganic substance such as a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, copper, molybdenum, And is preferably a compound that improves the adhesion of the insulating film. Specifically, known silane coupling agents and the like are also effective.

Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ- Methacryloxypropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyltrialkoxysilane,? -Methacryloxypropyltrialkoxysilane,? - Silane, and vinyltrialkoxysilane. Among these,? -Glycidoxypropyltrialkoxysilane and? -Methacryloxypropyltrialkoxysilane are more preferable, and? -Glycidoxypropyltrialkoxysilane is even more preferable, and 3-glycidoxypropyltrimethoxy Silane is even more preferred. These may be used alone or in combination of two or more.

The following compounds can also be preferably employed.

In the above, Ph is a phenyl group.

The (E) alkoxysilane compound in the photosensitive resin composition of the present invention is not particularly limited to these, and known ones can be used.

The content of the (E) alkoxysilane compound in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, per 100 parts by mass of the total solid content in the photosensitive composition.

(F) Crosslinking agent

The photosensitive resin composition of the present invention preferably contains a crosslinking agent, if necessary. By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made into a stronger film.

The crosslinking agent is not limited as long as it is crosslinked by heat (except for component A). For example, a compound having two or more epoxy groups or oxetanyl groups in the molecule, an alkoxymethyl group-containing crosslinking agent, a compound having at least one ethylenically unsaturated double bond, a block isocyanate compound and the like may be added in the following description.

The addition amount of the crosslinking agent in the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass relative to 100 parts by mass of the total solid content of the photosensitive resin composition desirable. When added in this range, a cured film excellent in mechanical strength and solvent resistance can be obtained. The crosslinking agent may be used in combination with a plurality of the crosslinking agents, in which case the crosslinking agents are all added to calculate the content.

&Lt; Compounds having two or more epoxy groups or oxetanyl groups in the molecule &

Specific examples of the compound having two or more epoxy groups in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, aliphatic epoxy resin and the like.

These are available as commercial products. For example, commercially available products such as JER157S70 and JER157S65 (manufactured by Mitsubishi Chemical Holdings Corporation), such as those described in Japanese Patent Laid-Open Publication No. 2011-221494, paragraph [0189].

In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S and EP-4011S (manufactured by Adeka Corporation), NC-2000, NC-3000, NC-7300, XD- , EX-412, EX-421, EX (manufactured by Adeka Corporation), DENACOL EX-611, EX-612, EX-614, EX-614B, EX-622, EX- EX-821, EX-821, EX-821, EX-821, EX-821, DLC-203, DLC-204, DLC-202, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, EX- (Produced by Nagase ChemteX Corporation), YH-300, YH-301, YH-302, YH-315, YH-324 and YH-325 CELLOXIDE 2021P, 2081, 3000, EHPE3150, EPOLEADGT400, SERUBINASU B0134, B0177 (manufactured by Daicel Corporation), and the like.

These may be used alone or in combination of two or more.

Among them, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, aliphatic epoxy and aliphatic epoxy resin are more preferable, and bisphenol A type epoxy resin is particularly preferable.

As specific examples of the compound having two or more oxetanyl groups in the molecule, ARON OXETANE OXT-121, OXT-221, OX-SQ and PNOX (manufactured by Toagosei Co., Ltd.) can be used.

Further, the compound containing an oxetanyl group is preferably used alone or in combination with a compound containing an epoxy group.

As the other crosslinking agent, there can be preferably used an alkoxymethyl group-containing crosslinking agent and at least one compound having an ethylenically unsaturated double bond described in paragraphs [0107] to [0108] of Japanese Patent Application Laid-Open Publication No. 2012-8223 The contents of which are incorporated herein by reference. As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated glycoluril is preferable.

&Lt; Block isocyanate compound >

In the photosensitive resin composition of the present invention, a block isocyanate compound may also be preferably employed as a crosslinking agent. The block isocyanate compound is not particularly limited as long as it is a compound having a block isocyanate group, but is preferably a compound having two or more block isocyanate groups in one molecule from the viewpoint of curability.

The block isocyanate group in the present invention is a group capable of forming an isocyanate group by heat, and for example, a group in which an isocyanate group is protected by reacting a blocking agent with an isocyanate group can be preferably exemplified. The block isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 to 250 캜.

The skeleton of the block isocyanate compound is not particularly limited and may be any of those having two isocyanate groups in one molecule and may be an aliphatic, alicyclic or aromatic polyisocyanate. For example, 2,4- Isocyanate, isocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4- Methylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,2'-diethyl Ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene di 1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylenediisocyanate, 3, 3'-methylene ditolylene-4,4'-diisocyanate, 4,4'-diphenyl ether diisocyanate, tetrachlorophenylenediisocyanate, norbornadiisocyanate, hydrogenated 1,3-xylylene diisocyanate, And isocyanate compounds such as 4-xylylene diisocyanate and compounds of a prepolymer type skeleton derived from these compounds can be suitably used. Of these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) are particularly preferable.

Examples of the parent structure of the block isocyanate compound in the photosensitive resin composition of the present invention include a burette type, an isocyanurate type, an adduct type, and a bifunctional prepolymer type.

Examples of the block agent forming the block structure of the block isocyanate compound include an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a mercaptan compound, an imidazole compound, . Among them, a block agent selected from an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, and a pyrazole compound is particularly preferable.

Examples of the oxime compounds include oxime and ketoxime. Specific examples thereof include acetoxime, formaldehyde, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.

Examples of the lactam compound include ε-caprolactam, γ-butyrolactam, and the like.

Examples of the phenol compound include phenol, naphthol, cresol, xylenol, halogen-substituted phenol, and the like.

Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.

Examples of the amine compound include a primary amine and a secondary amine, and may be an aromatic amine, an aliphatic amine, or an alicyclic amine, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.

Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, and methyl acetoacetate.

Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole, and the like.

Examples of the mercaptan compound include alkyl mercaptans, aryl mercaptans, and the like.

The block isocyanate compound which can be used in the photosensitive resin composition of the present invention is commercially available as, for example, CORONATE AP STABLE M, CORONATE 2503, 2515, 2507, 2513, 2555, MILLIONATE MS- (Manufactured by Mitsui Chemicals, Inc.), TAKENATE B-830, B-815N, B-820NSU, B-842N, B-846N, B- MF6060, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (Above, Asahi (Manufactured by Kasei Chemicals Corporation), DESMODUR BL1100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, SUMIDUR BL3175 .) Can be preferably used.

(G) Thinner

The photosensitive resin composition of the present invention preferably contains a sensitizer in combination with the photoacid generator (B) in order to accelerate the decomposition thereof. The sensitizer absorbs an actinic ray or radiation to become an electron-excited state. The sensitizer in the electron excited state comes into contact with the photoacid generator to generate electron transfer, energy transfer, heat generation, and the like. Accordingly, the photoacid generator decomposes by chemical change to generate an acid. Examples of preferred sensitizers include compounds having an absorption wavelength in any one of the wavelength ranges of 350 nm to 450 nm belonging to the following compounds.

Polynuclear aromatic compounds such as pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10- Anthracene, xanthone, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone (for example, xanthone, Tonnes), cyanines (e.g., thiacarbocyanine, oxacarbocyanine), merocyanines (e.g., merocyanine, carbomerocyanine), loadersocyanates, (Such as acridine orange, chloroflavin, acriflavine), acridones (such as acridone, acridine, acridine), acridine (for example, thionine, methylene blue, toluidine blue) Butyl-2-chloroacridone, 10-butylacridone), anthraquinones (for example, anthraquinone), squaryliums (for example, (For example, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (for example, 7-diethylamino 4- Methylcoumarin, 7-hydroxy4-methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolizine Lt; / RTI &gt;

Among these sensitizers, polynuclear aromatic compounds, acridones, styryls, base styryls and coumarins are preferable, and polynuclear aromatic compounds are more preferable. Among the polynuclear aromatic compounds, an anthracene derivative is most preferable.

The amount of the sensitizer added in the photosensitive resin composition of the present invention is preferably 0 to 1000 parts by mass, more preferably 10 to 500 parts by mass, more preferably 50 to 200 parts by mass, per 100 parts by mass of the photoacid generator of the photosensitive resin composition Is more preferable.

Two or more species may be used in combination.

(H) Basic compound

The photosensitive resin composition of the present invention may contain (H) a basic compound. (H) As the basic compound, any of those used as chemical amplification resistors can be selected and used. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include compounds described in paragraphs [0204] to [0207] of JP-A No. 2011-221494, the contents of which are incorporated herein by reference. N-cyclohexyl-N'-2- (4-morpholinyl) ethyl] thiourea may also be used.

The basic compounds usable in the present invention may be used singly or in combination of two or more kinds.

The content of the other basic compound (H) in the photosensitive resin composition of the present invention is preferably 0.001 to 3 parts by mass, more preferably 0.005 to 1 part by mass relative to 100 parts by mass of the total solid content in the photosensitive resin composition, It is more desirable to be negative.

(I) Surfactant

The photosensitive resin composition of the present invention may contain (I) a surfactant. As the (I) surfactant, any of anionic, cationic, nonionic or amphoteric surfactants may be used, but preferred surfactants are nonionic surfactants.

Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicones, and fluorine surfactants. (Manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), F TOP (manufactured by JEMCO Corporation), Megafac (manufactured by DIC Corporation), FLUORAD Ltd.), AsahiGuard, Surflon (manufactured by Asahi Glass Co., Ltd.), POLYFOX (manufactured by OMNOVA), and SH-8400 (Toray and Dow Corning Silicone).

In addition, when the surfactant contains the constituent unit A and the constituent unit B represented by the following general formula (I-1) and is tetrahydrofuran (THF) as a solvent, the weight in terms of polystyrene measured by gel permeation chromatography A preferred example is a copolymer having an average molecular weight (Mw) of 1,000 or more and 10,000 or less.

In general formula (I-1)

R ⁴⁰¹ and R ⁴⁰³ each represent a hydrogen atom or a methyl group, R ⁴⁰² represents a straight chain alkylene group having 1 to 4 carbon atoms and R ⁴⁰⁴ represents a hydrogen atom or a linear or branched alkyl group having 1 or more carbon atoms P represents an integer of not less than 4, and L represents an alkylene group of not less than 3 but not more than 6 carbon atoms, p and q are mass percentages indicating a polymerization ratio, p is a value of 10 mass% or more and 80 mass% , q represents a numerical value of 20 mass% or more and 90 mass% or less, R represents an integer of 1 or more and 18 or less, and s represents an integer of 1 or more and 10 or less,

It is preferable that L is a branched alkylene group represented by the following general formula (I-2). R ⁴⁰⁵ in the general formula (I-2) represents an alkyl group of 1 to 4 carbon atoms and is preferably an alkyl group of 1 to 3 carbon atoms from the viewpoint of compatibility and hygroscopicity against the surface to be coated, More preferably three or three alkyl groups. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by mass.

In general formula (I-2)

The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.

These surfactants may be used alone or in combination of two or more.

The amount of the surfactant (I) added to the photosensitive resin composition of the present invention is preferably 10 parts by mass or less, more preferably 0.001 parts by mass to 10 parts by mass, more preferably 0.01 parts by mass to 3 parts by mass relative to 100 parts by mass of the total solid content in the photosensitive resin composition It is more desirable to be negative.

(J) Antioxidant

The photosensitive resin composition of the present invention may contain an antioxidant. As the antioxidant, a known antioxidant may be contained. The addition of an antioxidant can prevent coloration of the cured film or reduce the film thickness reduction due to decomposition and has an advantage of excellent heat-resistant transparency.

Examples of such antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites, thiosulfates, And hydroxylamine derivatives. Among them, a phenol-based antioxidant, an amide-based antioxidant, a hydrazide-based antioxidant and a sulfur-based antioxidant are particularly preferable from the viewpoint of coloring of the cured film and reduction of the film thickness. These may be used singly or in combination of two or more kinds.

Examples of commercially available phenolic antioxidants include ADK STAB AO-15, ADK STAB AO-18, ADK STAB AO-20, ADK STAB AO-23, ADK STAB AO-30, ADK STAB AO- -40, ADK STAB AO-50, ADK STAB AO-51, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO- , ADK STAB PEP-24, ADK STAB PEP-36, ADK STABA-611, ADK STABA-612, ADK STABA-613, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP- STAB PAB-36Z, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 135A, ADK STAB 3010, ADK STAB TPP, ADK STAB CDA IRGANOX 1010FF, IRGANOX 1010, IRGANOX MD1024, IRGANOX 1035FF, IRGANOX (produced by Adeka Corporation), IRGANOX 245FF, IRGANOX 1010FF, IRGANOX 1035FF, IRGANOX 1035FF, 1035, IRGANOX 1098, IRGANOX 1330, IRGANOX 1520L, IRGANOX 3114, IRGANOX 1726, IRGAFOS 168 and IRGAMOD 295 (manufactured by BASF Ltd.). Among them, ADK STAB AO-60, ADK STAB AO-80, IRGANOX 1726, IRGANOX 1035 and IRGANOX 1098 can be suitably used.

The content of the antioxidant is preferably from 0.1 to 10 mass%, more preferably from 0.2 to 5 mass%, and particularly preferably from 0.5 to 4 mass%, based on the total solid content of the photosensitive resin composition. With this range, sufficient transparency of the film formed can be obtained, and sensitivity at the time of pattern formation becomes good.

Various ultraviolet absorbers, metal deactivators, and the like described in "New developments of polymer additive " (Nikkan Kogyo Shimbun) can be added to the photosensitive resin composition of the present invention as additives other than the antioxidant.

[Acid growth agent]

For the purpose of improving the sensitivity, the photosensitive resin composition of the present invention can use an acid growth agent.

The acid-proliferating agent usable in the present invention is a compound capable of generating an acid by an acid catalytic reaction to raise the concentration of an acid in the reaction system and stably exists in a state in which no acid exists. Such a compound accelerates the reaction in accordance with the progress of the reaction because at least one acid increases in a single reaction, but since the resulting acid itself causes self-decomposition, the strength of the acid generated here is the acid dissociation constant, pKa 3 or less, and particularly preferably 2 or less.

Specific examples of the acid proliferating agent include those described in paragraphs [0203] to [0223] of Japanese Patent Application Laid-Open No. 10-1508, paragraphs [0016] to [0055] of Japanese Patent Application Laid- 9-512498, page 39, line 12 to page 47, line 2, the contents of which are incorporated herein by reference.

Examples of the acid growth agent that can be used in the present invention include acids decomposed by an acid generated from an acid generator and having a pKa of 3 or less such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, Compounds which generate an acid can be mentioned.

Specifically,

And the like.

The content of the acid proliferating agent in the photosensitive composition is preferably from 10 to 1,000 parts by mass based on 100 parts by mass of the photoacid generator from the viewpoint of dissolution contrast between the exposed portion and the unexposed portion, more preferably from 20 to 500 parts by mass.

[Development promoter]

The photosensitive resin composition of the present invention may contain a development accelerator.

As the phenomenon promoter, mention may be made of paragraphs [0171] to [0172] of Japanese Patent Application Laid-Open Publication No. 2012-042837, the contents of which are incorporated herein by reference.

The development accelerator may be used alone or in combination of two or more.

The addition amount of the development accelerator in the photosensitive resin composition of the present invention is preferably from 0 to 30 parts by mass, more preferably from 0.1 to 20 parts by mass, and still more preferably from 0.5 to 5 parts by mass, relative to 100 parts by mass of the total solid content of the photosensitive composition, from the viewpoints of sensitivity and residual film- Most preferably 10 to 10 parts by mass.

As other additives, a thermal radical generator described in paragraphs [0120] to [0121] of Japanese Patent Application Laid-Open Publication No. 2012-8223, a nitrogen containing compound described in WO2011 / 136074A1, and a thermal acid generation system, Are incorporated into the specification.

&Lt; Preparation method of photosensitive resin composition >

Each component is further mixed in a predetermined ratio by an arbitrary method, and the mixture is stirred and dissolved to prepare a photosensitive resin composition. For example, it is also possible to prepare a solution in which the components are respectively dissolved in a solvent, and then mix them in a predetermined ratio to prepare a resin composition. The composition solution prepared as described above may be provided for use after filtration using a filter having a pore diameter of 0.2 mu m or the like.

[Method of manufacturing pattern]

Next, a method for producing the pattern of the present invention will be described.

The method for producing the cured film of the present invention preferably includes the following steps (1) to (5).

(1) a step of applying the photosensitive resin composition of the present invention onto a substrate;

(2) removing the solvent from the applied photosensitive resin composition;

(3) exposing the photosensitive resin composition from which the solvent has been removed by an actinic ray;

(4) developing the exposed photosensitive resin composition with an aqueous developing solution;

(5) A step of etching the substrate using the formed resist pattern as a mask.

Each step will be described below in order.

(1), it is preferable to apply the photosensitive resin composition of the present invention onto a substrate to form a wet film containing a solvent. It is preferable to clean the substrate subjected to alkali cleaning or plasma cleaning before applying the photosensitive resin composition to the substrate, and it is more preferable to treat the substrate surface with hexamethyldisilazane after the substrate cleaning. By carrying out this treatment, the adhesion of the photosensitive resin composition to the substrate tends to be improved. The method of treating the surface of the substrate with hexamethyldisilazane is not particularly limited, and for example, a method of exposing the substrate to hexamethyldisilazane vapor may be mentioned.

Examples of the substrate include an inorganic substrate, a resin, and a resin composite material. Examples of the substrate include 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, A metal substrate such as a tin film, Ni, Cu, Fe, or Al; Silicon substrates such as quartz, glass, silicon nitride film, silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon film, SOG, silicon wafers for manufacturing semiconductor devices, glass substrates for manufacturing liquid crystal devices; A polymer substrate such as paper, a polyester film, a polycarbonate film, a polyimide film, and other polymer substrates that can be used in an organic EL display device; A ceramic material, a Ti substrate, an Al substrate, or the like can be used. Among them, an ITO substrate, a molybdenum substrate, a silicon substrate, a Cu substrate, or an Al substrate is preferable in the present invention, more preferably an ITO substrate, a molybdenum substrate, or a silicon substrate.

The shape of the substrate may be a plate shape or a roll shape.

The coating method on the substrate is not particularly limited and methods such as a slit coating method, a spraying method, a roll coating method, a rotation coating method, a casting method, a slit-and-spin method and the like can be used. It is also possible to apply the so-called prewetting method as described in Japanese Patent Application Laid-Open No. 2009-145395.

The thickness of the wetting film when applied is not particularly limited, and it can be applied with a film thickness according to the application, but it is usually used in the range of 0.5 to 10 mu m.

In the solvent removing step of (2), the solvent is removed from the coated film by depressurization and / or heating to form a dried coating film on the substrate. The heating condition of the solvent removing step is preferably about 70 to 130 占 폚 for 30 to 300 seconds. When the temperature and the time are in the above range, the pattern adhesion tends to be better and the residue tends to be lowered.

In the exposure step of the step (3), the substrate provided with the coating film is irradiated with an actinic ray through a mask having a predetermined pattern. In this step, the photoacid generator is decomposed to generate acid. By the catalytic action of the generated acid, the acid-decomposable group contained in the coating film component is hydrolyzed to produce a carboxyl group or a phenolic hydroxyl group.

(436 nm), an i-ray (365 nm), an h-ray (405 nm), and the like can be used as an exposure light source by an active light beam, such as a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, Of an active ray having a wavelength of 300 nm or more and 450 nm or less can be preferably used. If necessary, the irradiation light may be adjusted by passing through a spectral filter such as a long wavelength cutoff filter, a short wavelength cutoff filter, or a bandpass filter.

As the exposure apparatus, various types of exposure apparatus such as a mirror projection apparatus, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.

Post-exposure heat treatment: Post Exposure Bake (hereinafter referred to as &quot; PEB &quot;) can be performed to accelerate the hydrolysis reaction in the acid-generated region. PEB can promote the generation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The temperature for PEB is preferably 30 占 폚 to 130 占 폚, more preferably 40 占 폚 to 110 占 폚, and particularly preferably 50 占 폚 to 100 占 폚.

However, the acid decomposable group in the present invention has a low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator due to exposure. In order to generate a carboxyl group or a phenolic hydroxyl group, A positive type image may be formed.

It is preferable that the developer used in the step (4) contains a basic compound. Examples of the basic compound include alkali metal hydroxide such as lithium hydroxide, sodium hydroxide and potassium hydroxide; Alkali metal carbonates such as sodium carbonate and potassium carbonate; Alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; Ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline hydroxide; An aqueous solution of sodium silicate, sodium metasilicate or the like can be used. An aqueous solution in which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added to the aqueous alkaline solution may be used as a developer.

The pH of the developing solution is preferably 10.0 to 14.0.

The development time is preferably 30 to 180 seconds, and the developing method may be any of immersion, dipping, and the like. After the development, washing with water for 30 to 90 seconds is carried out to form a desired pattern.

In the step (5), a method of etching the substrate using the resist pattern as a mask is not particularly limited, and a known method can be used.

The method for producing a pattern of the present invention may include (6) a step of peeling off the resist pattern. The method of peeling the resist pattern is not particularly limited, and a known method can be used. Further, the resist pattern may be removed by a plasma treatment or a chemical treatment.

[Coating film]

In the present invention, (4) the pattern corresponding to the unexposed area obtained by the development after the developing process is heated at a predetermined temperature, for example, 180 to 250 DEG C for a predetermined time , For example, a cured film such as a protective film or an interlayer insulating film excellent in heat resistance and hardness can be formed by heat treatment for 5 to 60 minutes in the case of a hot plate and 30 to 90 minutes in the case of an oven.

When the heat treatment is carried out, the transparency of the cured film can be improved by performing the heat treatment in a nitrogen atmosphere.

In addition, it is preferable to heat the substrate after re-exposure to the substrate formed with the patterned cured film by an actinic ray prior to the heat treatment.

That is, in order to form the cured film of the present invention, it is preferable to include a step of re-exposure by an actinic ray between the step of developing and the step of thermosetting.

The exposure in the step of re-exposure may be performed by the same means as the step of exposing, but in the step of re-exposure, it is preferable to perform the whole surface exposure on the side of the substrate where the film is formed by the photosensitive resin composition of the present invention. A preferable exposure amount of the step for re-exposure is 100 to 1,000 mJ / cm &lt; 2 &gt;.

[pattern]

The pattern of the present invention is a pattern obtained by using the resist pattern obtained by curing the photosensitive resin composition of the present invention as a mask and etching the substrate. The pattern of the present invention can be preferably used as an ITO pattern, a molybdenum pattern, or a silicon pattern, and can be 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 excellent in rectangularity can be obtained. Since the pattern of the present invention can be obtained by the method for producing a pattern of the present invention using the resist pattern, it is possible to perform microfabrication, and the organic EL display device and the liquid crystal display device can have high-quality display characteristics.

[Liquid crystal display device]

The liquid crystal display device of the present invention is characterized by including the cured film of the present invention.

As the liquid crystal display of the present invention, there is no particular limitation but a well-known liquid crystal display device having various structures other than those having a planarizing film or an interlayer insulating film formed using the photosensitive resin composition of the present invention.

For example, specific examples of a TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include an amorphous silicon TFT, a low-temperature polysilicon TFT, and an oxide semiconductor TFT. Since the cured film of the present invention is excellent in electric characteristics, it can be preferably used in combination with these TFTs.

As a liquid crystal driving method that can be adopted by the liquid crystal display of the present invention, twisted nematic (VA), VA (virtual alignment), IPS (in-place switching), FFS Compensated Bend) method.

In the panel structure, the cured film of the present invention can also be used in a COA (Color Filter on All) type liquid crystal display device. For example, the organic insulating film 115 of Japanese Patent Application Laid-Open No. 2005-284291, And can be used as the organic insulating film 212 of JP-A-346054.

Specific examples of the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method. It may also be polymer-oriented supported by the PSA (Polymer Sustained Alignment) technique described in Japanese Patent Application Laid-Open Nos. 2003-149647 and 2011-257734.

In addition, the photosensitive resin composition of the present invention and the cured film of the present invention are not limited to the above-mentioned applications and can be used for various purposes. For example, in addition to a planarizing film and an interlayer insulating film, a protective film for a color filter or a spacer for keeping the thickness of a liquid crystal layer in a liquid crystal display device constant, a microlens provided on a color filter in a solid- Can be used.

Fig. 1 is a conceptual cross-sectional view showing an example of an active matrix type liquid crystal display device 10. Fig. This color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on its back surface and the liquid crystal panel has TFTs corresponding to all the pixels disposed between two glass substrates 14, (16) are disposed on the substrate. An ITO transparent electrode 19 for forming a pixel electrode is wired through a contact hole 18 formed in the cured film 17 in each element formed on the glass substrate. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal layer 20 and a black matrix are arranged is provided.

The light source of the backlight is not particularly limited and a known light source can be used. For example, white LEDs, multicolor LEDs such as blue, red, and green, fluorescent lamps (cold cathode tubes), and organic ELs.

The liquid crystal display device may be a 3D (stereoscopic) type or a touch panel type. It can also be used as a flexible type, and can be used as a second interlayer insulating film 48 of JP-A-2011-145686 or an inter-phase insulating film 520 of JP-A-2009-258758.

[Organic EL display device]

The organic EL display device of the present invention is characterized by including the cured film of the present invention.

The organic EL 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 various known organic EL display devices and liquid crystal display devices having various structures .

For example, specific examples of a TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include an amorphous silicon TFT, a low-temperature polysilicon TFT, and an oxide semiconductor TFT. Since the cured film of the present invention is excellent in electric characteristics, it can be preferably used in combination with these TFTs.

2 is a conceptual diagram showing an example of an organic EL display device. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device and has a planarization film 4.

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 in a state of covering the TFT 1. A contact hole (not shown) is formed in the insulating film 3 and a wiring 2 (height 1.0 mu m) connected to the TFT 1 through the contact hole is formed on the insulating film 3 . The wiring 2 is for connecting the organic EL element formed in the TFT 1 or in a subsequent step to the TFT 1. [

The flattening layer 4 is formed on the insulating film 3 in a state in which the irregularities by the wiring 2 are buried in order to planarize the irregularities due to the formation of the wiring 2. [

On the planarizing film 4, a bottom-emission organic EL element is formed. That is, a first electrode 5 made of ITO is formed on the planarization film 4 by being connected to the wiring 2 through the contact hole 7. Also, the first electrode 5 corresponds to the anode of the organic EL element.

An insulating film 8 is formed so as to cover the edge of the first electrode 5. By providing this insulating film 8, a short circuit is prevented between the first electrode 5 and the second electrode formed in the subsequent step can do.

Further, a hole transport layer, an organic luminescent layer, and an electron transport layer are sequentially deposited through a desired pattern mask (not shown in Fig. 2), then a second electrode made of Al is formed on the entire upper surface of the substrate, An organic EL display device of an active matrix type in which an ultraviolet curing type epoxy resin is used to seal by bonding and the TFT 1 for driving each organic EL element is connected is obtained.

Since the photosensitive resin composition of the present invention is excellent in curability and cured film properties, the resist pattern formed by using the photosensitive resin composition of the present invention as a structural member of the MEMS device can be used as a separating wall, do. Examples of such MEMS devices include SAW filters, BAW filters, gyro sensors, micro-shutters for displays, image sensors, electronic paper, inkjet heads, biochips, and sealants. More specific examples are exemplified in Japanese Patent Publication Nos. 2007-522531, 2008-250200, and 2009-263544.

Since the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer 16 and the planarization film 57 shown in Fig. 2 of Japanese Patent Laid-Open Publication No. 2011-107476, Japanese Patent Application Laid- The bank layer 221 and the third interlayer insulating film 216b shown in Fig. 10 of Japanese Patent Application Laid-Open No. 2010-27591, the Japanese Patent Laid-Open No. 2000-27591, the separating wall 12 and the planarizing film 102 described in Fig. 4 (a) The second interlayer insulating film 125 and the third interlayer insulating film 126 shown in FIG. 4A of JP 2009-128577 A, the planarization film 12 described in FIG. 3 of JP 2010-182638 A, The isolation insulating film 14 and the like.

(Example)

Hereinafter, the present invention will be described in more detail by way of examples. The materials, the amounts used, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

In the following Synthesis Examples, the following symbols respectively represent the following compounds.

MAEVE: 1-ethoxyethyl methacrylate

MATHF: tetrahydro-2H-furan-2-yl methacrylate

PHS: Parahydroxy styrene

MAA: methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)

HEMA: hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

EDM: (diethylene glycol ethyl methyl ether) (manufactured by Toho Chemical Industry Co., Ltd.)

BzMA: (benzyl methacrylate) (manufactured by Wako Pure Chemical Industries, Ltd.)

(Synthesis Example 1: Synthesis of Polymer 1)

20 g of an alkali-soluble resin (VP-8000, manufactured by Nippon Soda Co., Ltd.) and 320 g of propylene glycol monomethyl ether acetate (PGMEA) were dissolved in a flask and subjected to vacuum distillation to remove water and PGMEA by azeotropic distillation. After confirming that the function was sufficiently lowered, 24 g of ethyl vinyl ether and 0.35 g of p-toluenesulfonic acid were added, and the mixture was stirred at room temperature for 1 hour. Thereto was added 0.28 g of triethylamine to terminate the reaction. Ethyl acetate was added to the reaction mixture, and the mixture was further washed with water. The ethyl acetate, water and azeotropic distillation of PGMEA were distilled off under reduced pressure to obtain Polymer 1 as an alkali-soluble resin protected with an acid-decomposable group. The weight average molecular weight of the obtained resin was 11,000. The polydispersity was 1.13.

The structure of Polymer 1 was a 1-ethoxyethyl protected product of p-hydroxystyrene / p-hydroxystyrene copolymer (30 mol% / 70 mol%).

(Synthesis Example 2: Synthesis of Polymer 2)

15.6 g of an alkali-soluble resin (VP-8000, manufactured by Nippon Soda Co., Ltd.) and 100 g of propylene glycol monomethyl ether acetate (PGMEA) were dissolved in a flask and distilled under reduced pressure to azeotropically remove water and PGMEA. After confirming that the function was sufficiently lowered, 2.7 g of 2,3-dihydrofuran and 0.015 g of p-toluenesulfonic acid were added, and the mixture was stirred at room temperature for 2 hours. Thereto, 0.090 g of triethylamine was added to terminate the reaction. Ethyl acetate was added to the reaction solution, which was then washed with water, and ethyl acetate and water were distilled off by distillation under reduced pressure to obtain Polymer 2 as a soluble resin with a protection ratio of 25 mol%. The weight average molecular weight of the obtained resin was 12,000. The polydispersity was 1.13.

The structure of Polymer 2 was a 2-tetrahydrofuranyl protected product of p-hydroxystyrene / p-hydroxystyrene copolymer (30 mol% / 70 mol%).

&Lt; Synthesis of Polymer 3 >

Polymer 3 was synthesized as follows.

And 0.5 parts of phenothiazine was added to 144.2 parts (2 mol equivalents) of ethyl vinyl ether. While the reaction system was cooled to 10 DEG C or lower, 86.1 parts (1 mol equivalent) of methacrylic acid was added dropwise and the mixture was stirred at room temperature (25 DEG C) for 4 hours . After 5.0 parts of pyridinium p-toluenesulfonate was added, the mixture was stirred at room temperature for 2 hours and allowed to stand at room temperature overnight. 5 parts of sodium hydrogencarbonate and 5 parts of sodium sulfate were added to the reaction mixture, and the mixture was stirred at room temperature for 1 hour. After insolubles were filtered off, the mixture was concentrated under reduced pressure at 40 ° C or lower. The yellow oil was distilled under reduced pressure to obtain a boiling point占 폚 / 7 mmHg fraction of 1-ethoxyethyl methacrylate (MAEVE) (134.0 parts) as a colorless oil.

(52.83 parts (0.3 mol equivalent), MAA (8.61 parts (0.1 mol equivalent)) and HEMA (26.03 parts (0.2 mol equivalent)) of the obtained methacrylic acid 1-ethoxyethyl (63.28 parts ) And EDM (110.8 parts) was heated at 70 캜 under a nitrogen stream. While stirring this mixed solution, a mixed solution of radical polymerization initiator V-65 (trade name, manufactured by Wako Pure Chemical Industries, Ltd., 4 parts) and EDM (100.0 parts) was added dropwise over 2.5 hours. After completion of the dropwise addition, the polymer was reacted at 70 DEG C for 4 hours to obtain an EDM solution (solid concentration: 40%) of the polymer.

The polymer 3 thus obtained had a weight average molecular weight of 15,000 as determined by gel permeation chromatography (GPC).

Polymer 4 was also synthesized in the same manner as in the synthesis of Polymer 3.

(Photo acid generator)

PAG-1: Synthesized according to the method described in paragraph [0108] of Japanese Patent Publication No. 2002-528451.

The Ts portion represents a tosyl group.

(Alicyclic epoxy compound)

C1: The following compound (manufactured by Daicel Chemical Industries, Ltd., product number: CELLOXIDE 2021P)

C2: The following compound (manufactured by Shin-Etsu Chemical Co., Ltd., product number: KBM-303)

C3: The following compound (manufactured by Daicel Chemical Industries, Ltd., product number: CELLOXIDE 2081)

C4: The following compound (manufactured by Daicel Chemical Industries, Ltd., product number: EPOLEAD GT-401)

C5: 157S65 (manufactured by Mitsubishi Chemical Corporation)

C6: The following compound (manufactured by Nagase ChemteX Corporation, product number: EX-321L)

(solvent)

PGMEA: Methoxypropyl acetate (manufactured by Showa Denko K. K.)

PGDA: 1,2-propanediol diacetate (boiling point 190 占 폚, manufactured by Daicel Corporation, part number: PGDA)

1,3-BGDA: 1,3-butanediol diacetate (boiling point 232 占 폚, manufactured by Daicel Corporation, part number: 1,3-BGDA)

1,6-HDDA: 1,6-hexanediol diacetate (boiling point: 260 占 폚, manufactured by Daicel Corporation, part number: 1,6-HDDA)

DRA-150: triacetin (boiling point: 260 占 폚, manufactured by Daicel Corporation, product number: DRA-150)

DPNB: dipropylene glycol-n-butyl ether (boiling point 229 캜, manufactured by Daicel Corporation, product number: DPNB)

BDGAC: diethylene glycol monobutyl ether acetate (boiling point: 247 캜, manufactured by Daicel Corporation, product number: DPNB)

(Sensitizer)

G-1 (manufactured by Kawasaki Kasei Chemicals Ltd., product number: 9,10-dibutoxyanthracene)

(Basic compound)

H-1: (manufactured by Toyokasei Co., Ltd., product number: CMTU)

(Adjustment of photosensitive resin composition)

Each component was dissolved and mixed so as to have the composition shown in the following table, and filtered with a filter made of polytetrafluoroethylene having a pore diameter of 0.2 m to obtain photosensitive resin compositions of Examples and Comparative Examples. The mixing ratio was as shown in the following table.

(A1) and (A2) were blended in the ratio (weight ratio) shown in the polymer table (A).

(B) Photoacid generator (A) The photoacid generator (A) is added in an amount of 3.0 wt%

· 100 parts by weight of the alicyclic epoxy compound (A) polymer was blended as described in the following table.

(D1) Solvent The total amount of the solvent was mixed as shown in the following table.

(D2) The solvent was prepared so that the non-volatile content thereof was 20% by weight based on the composition.

- Basic compound (A): 0.2 wt%

Amount (A): The amount of the sensitizer (A) relative to 100 parts by weight of the polymer is 3.0%

The following evaluations were performed on the photosensitive resin compositions of the respective examples and comparative examples obtained as described above.

&Lt; Evaluation of sensitivity &

Coated on a glass substrate subjected to cleaning and HMDS treatment to a film thickness of 1.3 mu m and exposed and developed through a mask to evaluate the sensitivity at an exposure amount at which a line and space pattern of 10 mu m was exactly 10 mu m as an optimum exposure amount. 3 or more is a practical level.

1: Requires exposure of 100 mJ / cm2 or more

2: Requires exposure of less than 50 mJ / cm 2 and less than 100 mJ / cm 2

3: Exposure amount of less than 20mJ / cm2 and less than 50mJ / cm2 is required

4: Exposure amount of not less than 10 mJ / cm 2 and not more than 20 mJ

5: exposure amount less than 10 mJ / cm &lt; 2 &gt;

&Lt; Evaluation of line width stability &

Washed and HMDS-treated glass substrate to a film thickness of 1.3 mu m, and exposed and developed at an exposure amount such that a line-and-space pattern of 10 mu m was exactly 10 mu m through the mask. The substrate with the line- The line width of 10 mu m was measured with an optical measuring instrument ZYGO New View 7200 (manufactured by ZYGO Corp.) at 10 points per substrate, and the standard deviation (?) Of the actual line width of 100 lines was calculated. The evaluation criteria are as follows, and three or more are practical levels.

1: standard deviation (sigma) of 0.4 mu m or more

2: a standard deviation (sigma) of not less than 0.2 mu m and not more than 0.4 mu m

3: a standard deviation (sigma) of not less than 0.15 mu m and not more than 0.25 mu m

4: a standard deviation (sigma) of not less than 0.1 mu m and not more than 0.15 mu m

5: Standard deviation (sigma) of less than 0.1 mu m

<Evaluation of resolution>

Coated on a glass substrate subjected to cleaning and HMDS treatment to a film thickness of 1.3 mu m and exposed and developed through a mask to obtain a resolution which is the smallest resolution of the line and space pattern. 3 or more is a practical level.

1: Resolution of 5 탆 or more

2: 3.0 μm resolved but 2.5 μm not resolved

3: 2.5 ㎛ resolved but 2.0 ㎛ resolved

4: 2.0 μm resolved but 1.5 μm not resolved

5: 1.5 ㎛ resolved

&Lt; Evaluation of rectangularity &

Washed and HMDS-treated glass substrate with a film thickness of 1.3 mu m, and exposed and developed with an exposure amount such that a line-and-space pattern of 10 mu m was exactly 10 mu m through the mask, Temperature bake for 3 minutes and measuring the taper angle of the L & S pixel of 3 mu m to make it rectangular. 3 or more is a practical level.

1: Taper angle less than 30 °

2: Taper angle is 30 ° or more and less than 45 °

3: Taper angle is more than 45 ° and less than 60 °

4: Taper angle is 60 ° or more and less than 75 °

5: Taper angle is more than 75 °

As shown in the above table, it was found that the photosensitive resin compositions of the respective Examples had excellent results in evaluation of sensitivity, resolution, and rectangularity in comparison with the photosensitive resin compositions of the respective comparative examples.

(Example 16)

<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 in a state of covering the TFT 1. Subsequently, a contact hole (not shown) was formed in the insulating film 3, and a wiring 2 (height 1.0 mu m) connected to the TFT 1 through the contact hole was formed on the insulating film 3 . This wiring 2 is for connecting the organic EL element formed in the TFT 1 or in a subsequent step to the TFT 1. [

In order to planarize the irregularities formed by the formation of the wirings 2, the flattening film 4 was formed on the insulating film 3 in the state of embedding the irregularities by the wirings 2. The formation of the planarization film 4 on the insulating film 3 is carried out by spin-coating the photosensitive resin composition described in Example 1 of JP-A No. 2009-98616 on a substrate and pre-baking (90 占 폚 for 2 minutes) on a hot plate After irradiating i-line (365 nm) with 45 mJ / cm 2 (illuminance of 20 mW / cm 2) using a high-pressure mercury lamp on a mask, the pattern was formed by developing with an aqueous alkali solution and heat treatment was conducted at 230 ° C for 60 minutes.

The coating properties at the time of applying the photosensitive resin composition were good, and no wrinkles or cracks were observed in the cured films obtained after exposure, development and firing. The average step of the wiring 2 was 500 nm, and the thickness of the planarization film 4 was 2,000 nm.

Subsequently, a bottom-emission type organic EL device was formed on the obtained planarization film 4. First, a first electrode 5 made of ITO was formed on the flattening film 4 by connecting it to the wiring 2 through the contact hole 7. [ Thereafter, the photosensitive resin composition of Example 1 was spin-coated on an ITO substrate and pre-baked (90 占 폚 for 2 minutes) on a hot plate. Then, an i-line (365 nm) was irradiated on the mask with a high pressure mercury lamp at 20 mJ / Irradiated at an illuminance of 20 mW / cm 2), and then developed with an aqueous alkaline solution to form a pattern. Thereafter, post-baking heat treatment was performed at 140 캜 for 3 minutes before the etching step. ITO patterning was carried out by wet etching by immersing the resist pattern in a ITO etchant (3% oxalic acid aqueous solution) at 40 DEG C for 1 minute using the resist pattern as a mask. Subsequently, the resist pattern was peeled by immersing the resist in a resist stripping solution (MS2001, manufactured by Fujifilm Electronic Materials Co., Ltd.) at 70 DEG C for 7 minutes. The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

Then, an insulating film 8 having a shape covering the edge of the first electrode 5 was formed. As the insulating film 8, the insulating film 8 was formed in the same manner as above using the photosensitive resin composition described in Example 1 of JP-A-2009-98616. 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 step.

Further, a hole transporting layer, an organic light emitting layer, and an electron transporting layer were sequentially evaporated through a desired pattern mask in a vacuum evaporation apparatus. Then, a second electrode made of Al was formed on the entire upper surface of the substrate. The obtained substrate was taken out from the evaporator, and sealed by using a sealing glass plate and an ultraviolet curable epoxy resin.

As described above, an organic EL display device having a matrix-type ITO pattern in which TFTs 1 for driving the organic EL elements were connected to each organic EL element was obtained. It was found that the organic EL display device exhibits good display characteristics and is highly reliable when a voltage is applied through a driving circuit.

(Example 17)

<Liquid Crystal Display Device>

A liquid crystal display device having an ITO pattern was produced by the following method.

In the active matrix type liquid crystal display device shown in Fig. 1 of Japanese Patent No. 3321003, the pixel electrode 4 was formed using the photosensitive resin composition of Example 1 as a mask, and a liquid crystal display device of Example 17 was obtained .

That is, the pixel electrode 4 was formed in the same manner as in the method of forming the first electrode 5 of the organic EL display device in Example 16.

It was found that when a driving voltage was applied to a liquid crystal display device having the obtained ITO pattern, the liquid crystal display device exhibited good display characteristics and was highly reliable.

1: TFT (thin film transistor) 2: wiring
3: insulating film 4: planarization 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: curing film 18: contact hole
19: ITO transparent electrode 20: liquid crystal
22: Color filter

Claims (14)

A polymer component A1 comprising a polymer having a structural unit a1 represented by the following general formula 1,
Photoacid generator B,
Alicyclic epoxy compound C, and
A solvent D1 containing two or more acetate structures in the molecule,
Wherein the alicyclic epoxy compound (C) is a compound represented by the following general formula (I);

Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ¹ and R ² is an alkyl group or an aryl group; R ³ represents an alkyl group or an aryl group, R ¹ or R ² and R ³ may be connected to form a cyclic ether; And R ⁴ represents a hydrogen atom or a methyl group.

[In the general formula (I), n represents an integer of 1 to 4;
R ¹ represents an organic group having 1 to 15 carbon atoms, and the organic group is a hydrocarbon group or a group formed by combining at least one of hydrocarbon group, -O-, -CO-, -S-, and -NR-, A hydrogen atom or an alkyl group having 1 to 7 carbon atoms. delete The method according to claim 1,
Wherein n in the compound represented by the general formula (I) is 1 or 2. 2. The photosensitive resin composition according to claim 1, The method according to claim 1,
Further comprising a polymer component A2 having a constituent unit a4 having a protected carboxyl group protected with an acid-decomposable group. 5. The method of claim 4,
Wherein the structural unit a4 is a structural unit represented by the following general formula A2 ';

Wherein at least one of R ¹ and R ² is an alkyl group or an aryl group, R ³ is an alkyl group or an aryl group, R ¹ and R ² are each independently a hydrogen atom, an alkyl group or an aryl group, R ¹ or R ² and R ³ may be connected to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or an arylene group. The method according to claim 1,
Wherein the content of the alicyclic epoxy compound (C) is 0.05 to 5% by mass relative to the total solid content. The method according to claim 1,
A solvent D1 containing two or more acetate structures in the molecule and a solvent D1 containing two or more acetate structures in the molecule and a solvent D2 different from the solvent D1. The method according to claim 1,
Wherein the solvent D1 containing two or more acetate structures in the molecule has a boiling point of 130 占 폚 or more and less than 300 占 폚. The method according to claim 1,
Wherein the content of the solvent D1 containing two or more acetate structures in the molecule is 1 to 10% by mass of the photosensitive resin composition. A step of applying the photosensitive resin composition described in claim 1 on at least one surface of a substrate,
A step of volatilizing the organic solvent by drying to form a photosensitive resin composition layer,
A step of exposing the photosensitive resin composition layer,
And a step of developing the exposed photosensitive resin composition layer. 11. The method of claim 10,
A step of performing etching using the formed pattern as an etching resist, and a step of removing the pattern by a plasma treatment or a chemical treatment. A cured film characterized by being formed by curing the photosensitive resin composition according to claim 1. A manufacturing method of an organic EL display device, characterized by comprising the method of manufacturing a pattern according to claim 10. A manufacturing method of a liquid crystal display device, which comprises the manufacturing method of a pattern according to claim 10.

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