TW201413379A - Photosensitive resin composition, method for manufacturing pattern using the same, cured film, method for manufacturing organic EL display device and method for manufacturing liquid crystal display device - Google Patents

Abstract

The invention provides a photosensitive resin composition excellent in sensitivity, line width stability, resolution and rectangular properties. The photosensitive resin composition contains: (A1) a polymer constituent including a polymer having a constitutional unit (a1) represented by General Formula (1) below; (B) a photoacid generator; (C) an alicyclic epoxy compound and (D) a solvent containing two or more acetate structures in a molecule (In the General Formula (1), R1 and R2 respectively and independently represents a hydrogen atom, an alkyl group or an aryl group, at least any one of R1 and R2 is the alkyl group or the aryl group; R3 represents the alkyl group or the aryl group, R1 or R2 could be connected to R3 to form a cyclic ether; R4 represents the hydrogen atom or a methyl group).

Description

Photosensitive resin composition, method for producing pattern using the same, cured film, method for producing organic EL display device, and method for producing liquid crystal display device

The present invention relates to a photosensitive resin composition and a method of producing a pattern using the same. Further, there is an organic electroluminescence (EL) display device or a method for producing a liquid crystal display device including the above-described pattern production method, and a pattern produced by the pattern production method. More specifically, the present invention relates to a positive photosensitive resin composition suitable for forming a resist layer of an electronic component such as a liquid crystal display device or an organic EL display device, and a method for producing a pattern using the same.

A metal wiring pattern such as an indium tin oxide (ITO) film in which a pattern is formed is provided in an organic EL display device or a liquid crystal display device. In the pattern formation of the ITO film or the like, a method is known in which a photosensitive resin composition is applied onto an ITO film, and a solvent is removed to expose and develop the film. The pattern is etched as a mask to perform processing.

Further, in recent years, in order to set high-definition display characteristics of an organic EL display device or a liquid crystal display device, high resolution of ITO processing is required. In order to perform high-fine microfabrication of ITO, it is required to exhibit high resolution of a photosensitive resin composition which functions as a mask during etching. For this reason, a photosensitive resin composition having a high-definition and fine pattern shape has been studied (for example, Japanese Patent Laid-Open No. Hei 9-325473, Japanese Patent Application Laid-Open No. Hei No. Hei 10-326015, and the like).

However, with the development of technology in recent years, a photosensitive resin composition having further improved sensitivity, line width stability, resolution, and rectangularity is required. The present invention has been made to solve the above-described problems, and an object of the invention is to provide a photosensitive resin composition having further improved sensitivity, line width stability, resolution, and rectangularity.

Based on the above situation, the inventors of the present application conducted active research and found that sensitivity, line width stability, resolution, and rectangularity can be improved by including a predetermined polymer, an alicyclic epoxy compound, and a predetermined solvent. Sexuality to complete the present invention.

Specifically, the above problem is solved by the following means <1>, preferably by <2> to <13>.

<1> A photosensitive resin composition comprising: (A1) a polymer component, comprising a polymer comprising a structural unit (a1) represented by the following formula (1); (B) a photoacid generator; C) an alicyclic epoxy compound; and (D1) a solvent having two or more acetate structures in the molecule;

(In the 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; and R ³ represents an alkyl group or an aromatic group; A group, R ¹ or R ² may be bonded to R ³ to form a cyclic ether; R ⁴ represents a hydrogen atom or a methyl group).

The photosensitive resin composition as described in <1>, wherein the (C) alicyclic epoxy compound is a compound represented by the following formula (I):

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

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

The photosensitive resin composition as described in any one of <1> to <3>, Further, the polymer component (A2) is contained, and the polymer component (A2) includes a constituent unit (a4) having a protective carboxyl group protected by an acid-decomposable group.

The photosensitive resin composition as described in <4>, wherein the structural unit (a4) is a structural unit represented by the following general formula (A2'):

(In the formula (A2'), 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, and R ³ represents an alkyl group or An aryl group, R ¹ or R ² may be bonded to R ³ to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or an extended aryl group.

The photosensitive resin composition according to any one of the above-mentioned, wherein the content of the (C) alicyclic epoxy compound is 0.05% by mass to 5% based on the total solid content. quality%.

The photosensitive resin composition as described in any one of the above-mentioned (D1) contains the solvent of the above-mentioned (D1) molecule containing two or more acetate structures, and the (D1) molecule mentioned above. Another solvent (D2) having a solvent containing two or more acetate structures.

The photosensitive resin composition of any one of the above-mentioned (D1), wherein the solvent of the (D1) molecule containing two or more acetate structures has a boiling point of 130 ° C or more and less than 300. °C.

The photosensitive resin composition according to any one of the above aspects, wherein the content of the solvent containing two or more acetate structures in the molecule (D1) is the photosensitive resin composition. 1% by mass to 10% by mass.

<10> A method of producing a pattern, comprising: (1) a step of applying the photosensitive resin composition according to any one of <1> to <9> on at least one side of the substrate; (2) a step of drying the organic solvent to form a photosensitive resin composition layer; (3) exposing the photosensitive resin composition layer; and (4) developing the exposed photosensitive resin composition layer A step of.

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

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

<13> An organic EL display device or a method of manufacturing a liquid crystal display device, comprising the method for producing a pattern according to <10> or <11>.

By the present invention, a high sensitivity and line width stability and resolution can be provided. And a photosensitive resin composition excellent in rectangularity.

1‧‧‧TFT (thin film transistor)

2‧‧‧Wiring

3‧‧‧Insulation film

4‧‧‧Flat film

5‧‧‧First electrode

6‧‧‧ glass substrate

7‧‧‧Contact hole

8‧‧‧Insulation film

10‧‧‧Liquid crystal display device

12‧‧‧Backlight unit

14, 15‧‧‧ glass substrate

16‧‧‧TFT

17‧‧‧ hardened film

18‧‧‧Contact hole

19‧‧‧ITO transparent electrode

20‧‧‧LCD

22‧‧‧Color filters

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

FIG. 2 is a conceptual diagram showing an example of a liquid crystal display device. A schematic cross-sectional view showing an active matrix substrate in a liquid crystal display device, having a cured film 17 as an interlayer insulating film.

Hereinafter, the contents of the present invention will be described in detail. In addition, the "~" in the specification of the present application is used in the meaning of including the numerical values described before and after the lower limit value and the upper limit value. Further, the organic EL display device in the present invention means an organic electroluminescence display device. The "polydispersity" in the present invention means the value of Mw/Mn.

Further, in the expression of the group (atomic group) in the present specification, the unsubstituted and unsubstituted expressions are not described as including not only a group having no substituent but also a group having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

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

The photosensitive resin composition of the present invention (hereinafter sometimes referred to as "the composition of the present invention") is characterized by comprising: (A1) a polymer component, and comprising a constituent unit represented by the following formula (1) (a1) a polymer; (B) a photoacid generator; (C) an alicyclic epoxy compound; and (D1) a solvent having two or more acetate structures in the molecule.

(In the 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; and R ³ represents an alkyl group or an aromatic group; a group, R ¹ or R ² may be bonded to R ³ 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 composition>

The photosensitive resin composition of the present invention contains (A1) a polymer component including the structural unit (a1) represented by the following general formula (1) as the polymer component (A). (A1) The polymer component may also contain a polymer other than the constituent unit (a1) represented by the formula (1). Further, the polymer component (A) preferably includes (A2) a constituent unit (a4) having a protective carboxyl group protected by an acid-decomposable group.

Hereinafter, the polymer components will be described.

<<Polymer composition (A1)>>

The (A1) polymer component in the present invention is a polymer component containing a polymer including the structural unit (a1) represented by the general formula (1). When the component (A1) includes the constituent unit (a1), a photosensitive resin composition having excellent resolution and squareness can be obtained.

(In the 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; and R ³ represents an alkyl group or an aromatic group; a group, R ¹ or R ² may be bonded to R ³ 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 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group may have a substituent. In addition, the alkyl group can Any of a straight chain, a branched chain, and a cyclic group is preferably a linear alkyl group. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a tert-butyl group, a pentyl group, a hexyl group or a cyclohexyl group.

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 particularly preferably an aryl group having 6 to 10 carbon atoms. The aryl group may have a substituent. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group and the like.

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, and a halogen atom. (fluorine atom, chlorine atom, bromine atom, iodine atom) and the like. These substituents may further have a substituent.

In these groups, 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 hydrogen. atom.

R ³ represents an alkyl group or an aryl group. The alkyl group and the aryl group represented by R ³ have the same meanings as the alkyl group and the 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 bonded to 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 a 3-membered ring to a 6-membered ring, more preferably a cyclic ether having a 5-membered ring to a 6-membered ring.

In the following, 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.

In view of the high sensitivity, the (A1) polymer component preferably contains a polymer including the structural unit (a2) represented by the following formula (2) in addition to the constituent unit (a1).

(In the 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- or o-, preferably bonded to the para position.

The constituent unit represented by the formula (2) is preferably 5.0 mol% to 30 mol%, more preferably 10 mol% to 20 mol%, of the constituent unit of the polymer component (A1). If it is less than the above amount, the effect cannot be obtained, and if it is too large, the sensitivity is excessively high, and the problem that the exposure process latitude is narrowed.

In the constituent unit of the polymer (A1), represented by the formula (1) The constituent unit is preferably 5 mol% to 40 mol%, more preferably 10 mol% to 40 mol%, more preferably 20 mol% to 35 mol% of the constituent unit of the polymer component of (A1). .

The protective ratio of the polymer (A1) is preferably from 1% to 60%, more preferably from 5% to 50%, particularly preferably from 10% to 40%. By setting it as the said range, image difference, sensitivity, and resolution are favorable. The protection ratio refers to the molar ratio of the group to be protected when the total structural unit in the (A1) polymer is 100 mol%.

The weight average molecular weight (Mw) of the above (A1) polymer is preferably in the range of from 2,000 to 15,000, more preferably from 5,000 to 12,000, still more preferably from 7,500 to 12,000. By setting it as 2000 or more, it is obtained that the formed pixel can maintain the squareness effect after heating by post-baking, and when it is set to 15000 or less, sensitivity and post-exposure delay (Post Exposure Delay, PED) are obtained. ) The effect of improved features. Here, the weight average molecular weight is defined by a polystyrene equivalent value of gel permeation chromatography.

The polydispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the above (A1) polymer is preferably from 1.0 to 4.0, more preferably from 1.5 to 3.5, still more preferably from 2.0 to 3.0. By setting it as the said range, the rectangular shape is favorable.

<<Polymer composition (A2)>>

The photosensitive resin composition of the present invention may contain (A2) a polymer component in addition to the (A1) polymer component. Preferably, the (A2) polymer component includes a constituent unit (a4) having a protective carboxyl group protected by an acid-decomposable group. Here, the acid-decomposable group means a functional group which can be decomposed in the presence of an acid.

The polymer component in the composition of the present invention is preferably alkali-insoluble, and is preferably an alkali-decomposable group when the acid-decomposable group of the structural unit represented by the formula (A2') is decomposed. Soluble resin. A constituent unit having a protective carboxyl group having a carboxyl group protected by an acid-decomposable group can be decomposed to form a carboxyl group by using an acid. Here, the term "alkali solubility" in the present invention means a coating film (thickness) of the compound (resin) formed by applying a solution of the compound (resin) to a substrate and heating at 90 ° C for 2 minutes. 3 μm) The dissolution rate of the 0.4% tetramethylammonium hydroxide aqueous solution at 23 ° C is 0.01 μm / sec or more, and the term "alkali-insoluble" means that the solution of the compound (resin) is applied onto the substrate. The coating film (thickness: 3 μm) of the compound (resin) formed by heating at 90 ° C for 2 minutes had a dissolution rate of 0.4% tetramethylammonium hydroxide aqueous solution at 23 ° C of less than 0.01 μm / sec.

The constituent unit having a protective carboxyl group which is protected by an acid-decomposable group, and a constituent unit having a protective carboxyl group protected by an acid-decomposable group, as described in paragraphs 0021 to 0055 of JP-A-2012-155288, The constituent unit having a protective carboxyl group protected by an acid-decomposable group described in paragraphs 0020 to 0052 of JP-A-2012-133091 is incorporated herein by reference. Among them, the (A2) polymer component preferably includes a polymer component constituting the unit (a4), and the acid group having the structure represented by the following formula (A2') is protected by an acid-decomposable group. Group. The acid group in the present invention means a proton dissociative group having a pKa of less than 7. The acid group is usually incorporated into a polymer using a monomer capable of forming an acid group as a constituent unit containing an acid group. When such a structural unit containing an acid group is contained in a polymer, it tends to be easily dissolved in an alkaline developing solution. When the component (A2) includes the constituent unit (a4), a photosensitive resin composition having an extremely high sensitivity can be obtained.

(In the formula (A2'), 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, and R ³ represents an alkyl group or An aryl group, R ¹ or R ² may be bonded to R ³ to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or an extended aryl group.

When R ¹ and R ² are an alkyl group, the number of carbon atoms is preferably an alkyl group of 1 to 10. In the case where R ¹ and R ² are an aryl group, 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 an alkyl group having 1 to 6 carbon atoms.

X ⁰ represents a single bond or an extended aryl group, preferably a single bond.

A preferred specific example of the constituent unit represented by the formula (A2') can be exemplified by the following constituent unit. Further, R represents a hydrogen atom or a methyl group.

The constituent unit represented by the formula (A2') is preferably 10 mol% to 80 mol%, more preferably 20 mol% to 80 mol%, more preferably 20 mol% to 80 mol% of the constituent unit of the polymer component (A2). 30 mole %~70 mole%.

In the constituent unit constituting the polymer component (A2), the content of the other constituent unit is preferably 60 mol% or less, more preferably 50 mol% or less, and particularly preferably 40 mol% or less. The lower limit value may be 0 mol%, and may be, for example, 1 mol% or more, and may be 5 mol% or more. When it is in the range of the above numerical values, the properties of the cured film obtained from the photosensitive resin composition become good.

The protective ratio of the polymer component (A2) is preferably from 1% to 60%, more preferably from 5% to 50%, particularly preferably from 10% to 40%. With the above range, the sensitivity is improved, and the difference in solubility (discrimination) between the exposed portion and the unexposed portion is improved. The protection ratio refers to the molar ratio of the group to be protected when the total structural unit in the polymer component (A2) is 100 mol%.

The weight average molecular weight (Mw) of the above (A2) polymer component is preferably in the range of from 2,000 to 15,000, more preferably from 5,000 to 12,000, still more preferably from 7,500 to 12,000. By setting it to 2000 or more, the formed pixels are obtained by post-baking After the heating, the effect of the rectangular shape can be maintained, and by setting it to 15,000 or less, the effect of improving the sensitivity and the PED characteristics can be obtained. Here, the weight average molecular weight is defined by a polystyrene equivalent value of gel permeation chromatography.

The polydispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the above (A2) polymer component is preferably from 1.0 to 4.0, more preferably from 1.5 to 3.5, still more preferably from 2.0 to 3.0. By setting it as the said range, it is excellent in rectangular shape.

- Ratio of (A1) component to (A2) component -

The photosensitive resin composition of the present invention preferably contains the component (A1) and the component (A2) as a polymer component. The quality of these ingredients is preferably 1:6~6:1, especially 2:5~8:1. By setting it as the said range, the effect of this invention is exhibited more effectively.

<<Polymer composition>>

In the present invention, the component (A) may include other constituent units (a3) other than the constituent units, in addition to the constituent unit (a1), the constituent unit (a2), and the constituent unit (a4). These constituent units may include either or both of the polymer component (A1) and the polymer component (A2). Further, the polymer component (A3) different from the polymer component (A1) or the polymer component (A2) may be contained, and the polymer component (A3) substantially does not contain the constituent unit (a1) and the constituent unit (a2). And the constituent unit (a4), but includes other constituent units (a3). The polymer component is different from the polymer component (A1) or the polymer component (A2), and the polymer component substantially does not contain the constituent unit (a1), the constituent unit (a2), and the constituent unit (a4). In the case of including other constituent units (a3), In the polymer component, the blending amount of the polymer component is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass or less.

The constituent unit (monomer) which is another constituent unit (a3) is not particularly limited, and examples thereof include styrene, alkyl (meth)acrylate, cyclic alkyl (meth)acrylate, and (methyl). An aryl acrylate, an unsaturated dicarboxylic acid diester, a bicyclic unsaturated compound, a maleimide compound, an unsaturated aromatic compound, a conjugated diene compound, an unsaturated monocarboxylic acid, Saturated dicarboxylic acid, unsaturated dicarboxylic anhydride, other unsaturated compounds. Further, as will be described later, a constituent unit having an acid group may also be included. The monomers which are other constituent units (a3) may be used singly or in combination of two or more.

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

In the total polymer component in the composition of the present invention, the proportion of the constituent unit having a pKa of 9 or more is preferably 10 mol% to 80 mol%, preferably 20 mol% to 70 mol%. Further, in the total polymer component in the composition of the present invention, the proportion of the constituent unit having a pKa of 5 or less is preferably 0 mol% to 20 mol%, preferably 5 mol% to 10 mol%. By using a large amount of a weak acid-containing constituent unit, even if a relatively strong alkali developing solution (for example, a 2.38% aqueous TMAH solution having a pH of more than 13) is used for development, the polymer is difficult to swell in the developing solution, and the film is not developed. Dissolution development is carried out at an appropriate speed. As a result, the formed pattern becomes more favorable. In addition, by forming a unit containing a small amount of strong acid of 20% or less, it is possible to form a map with higher sensitivity. case.

<(B) Photoacid generator>

The photosensitive resin composition of the present invention contains (B) a photoacid generator. The photoacid generator (also referred to as "(B) component") used in the present invention is preferably a compound which generates an acid by inducing an actinic ray having a wavelength of 300 nm or more, preferably 300 to 450 nm, but It is not limited to this chemical structure. In addition, the photoacid generator which does not directly induce the actinic ray having a wavelength of 300 nm or more is a compound which generates an acid by inducing an actinic ray having a wavelength of 300 nm or more by using it together with a sensitizer. It can be preferably used in combination with a sensitizer. The photoacid generator used in the present invention is preferably a photoacid generator which produces an acid having a pKa of 4 or less, more preferably a photoacid generator which produces an acid having a pKa of 3 or less, and preferably has a pKa of 2 or less. Acid photoacid generator.

Examples of the photoacid generator include trichloromethyl-s-triazine, sulfonium or phosphonium salt, quaternary ammonium salt, diazomethane compound, sulfhydryl sulfonate compound, and sulfonate compound. Wait. Among these compounds, an oxime sulfonate compound is preferably used from the viewpoint of insulating properties. These photoacid generators may be used alone or in combination of two or more. Specific examples of the trichloromethyl-s-triazine, the diarylsulfonium salt, the triarylsulfonium salt, the quaternary ammonium salt, and the diazomethane derivative can be exemplified by Japanese Patent Laid-Open Publication No. 2011-221494. The compound described in paragraph number 0083 to paragraph number 0008.

The oxime sulfonate compound, that is, the compound having an oxime sulfonate structure, is preferably a compound containing an oxime sulfonate structure represented by the following formula (B1).

(In the formula (B1), R ²¹ represents an alkyl group or an aryl group; a wavy line indicates a bond with another group.)

Any one of the groups may be substituted, and the alkyl group in R ²¹ may be linear, branched or cyclic. The permitted substituents will be described below.

The alkyl group of R ²¹ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R ²¹ may be an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (including a bridged ring such as 7,7-dimethyl-2-oxonorbornyl) The alicyclic group is preferably substituted with a bicycloalkyl group or the like.

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

The above compound containing the oxime sulfonate structure represented by the above formula (B1) is also preferably an oxime sulfonate compound represented by the following formula (B2).

(In the formula (B2), R ⁴² represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group or a halogen atom, m4 represents an integer of 0 to 3, and when m4 is 2 or 3, a plurality of X may be the same It can be different.)

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

The alkoxy group as X 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 formula (B2), it is particularly preferred that m4 is 1, X is a methyl group, the substitution position of X is an ortho position, and R ⁴² is a linear alkyl group having a carbon number of 1 to 10, and 7,7-dimethylene. A compound of phenyl-2-oxo norbornylmethyl or p-toluyl.

The compound containing the oxime sulfonate structure represented by the above formula (B1) is also preferably an oxime sulfonate compound represented by the following formula (B3).

(In the formula (B3), R ⁴³ has the same meaning as R ⁴² in the formula (B2), and X ¹ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a cyano group. Or nitro, n4 represents an integer from 0 to 5.)

R ⁴³ in the above formula (B3) is preferably: methyl, ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, all Fluorine-n-butyl, p-tolyl, 4-chlorophenyl or pentafluorophenyl, particularly preferably n-octyl.

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 above formula (B3) include α-(methylsulfonyloxyimino)benzylcarbonitrile and α-(ethylsulfonyloxyimino)benzylcarbonitrile. --(n-propylsulfonyloxyimino)benzylcarbonitrile, α-(n-butylsulfonyloxyimino)benzylcarbonitrile, α-(4-toluenesulfonyloxyimino) Benzonitrile, α-[(methylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile, α-[(ethylsulfonyloxyimino)-4-methoxybenzene Acetonitrile, α-[(n-propylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile, α-[(n-butylsulfonyloxyimino)-4-methoxy Phenyl phenyl] acetonitrile, α-[(4-toluenesulfonyloxyimino)-4-methoxyphenyl]acetonitrile.

Specific examples of the preferred oxime sulfonate compound include the following compounds (i) to (viii), and the like, and may be used alone or in combination of two or more. The compound (i) to the compound (viii) can be obtained as a commercial product. Further, it can also be used in combination with other types of (B) photoacid generators.

The compound containing the oxime sulfonate structure represented by the above formula (B1) is also preferably a compound represented by the following formula (OS-1).

In the above formula (OS-1), R ¹⁰¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a decyl group, an amine carbaryl group, an amine sulfonyl group, a sulfo group, a cyano group, or the like. Aryl, or heteroaryl. R ¹⁰² represents an alkyl group or an aryl group.

X ¹⁰¹ represents -O-, -S-, -NH-, -NR ¹⁰⁵ -, -CH ₂ -, -CR ¹⁰⁶ H-, or -CR ¹⁰⁵ R ¹⁰⁷ -, and R ¹⁰⁵ to R ¹⁰⁷ represent an alkyl group or an aromatic group. base.

R ¹²¹ to R ¹²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amine group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, a decylamino group, a sulfo group or a cyano group. Or aryl. Two of R ¹²¹ to R ¹²⁴ may be bonded to each other to form a ring.

R ¹²¹ to R ^{124 are} preferably a hydrogen atom, a halogen atom, and an alkyl group. Further, it is preferable to exemplify a state in which at least two of R ¹²¹ to R ¹²⁴ are bonded to each other to form an aryl group. Among them, from the viewpoint of sensitivity, it is preferred that all of R ¹²¹ to R ¹²⁴ are hydrogen atoms.

The functional groups described may each further have a substituent.

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

In the above formula (OS-2), R ¹⁰¹ , R ¹⁰² and R ¹²¹ to R ¹²⁴ have the same meanings as in the formula (OS-1), and preferred examples are also the same.

In these preferred embodiments, it is more preferred that R ¹⁰¹ in the above formula (OS-1) and the above formula (OS-2) is a cyano group or an aryl group, and it is most preferred from the above formula ( The aspect represented by OS-2) and R ¹⁰¹ is a cyano group, a phenyl group or a naphthyl group.

Further, the steric structure (E, Z, etc.) of the hydrazine or benzothiazole ring in the above sulfonate compound may be either a mixture or a mixture.

Specific examples of the compound represented by the above formula (OS-1) which can be suitably used in the present invention include the compounds described in Paragraph No. 0128 to Paragraph No. 0132 of JP-A-2011-221494 (exemplified compound b- 1 to the exemplified compound b-34), but the present invention is not limited thereto.

In the present invention, the compound containing the oxime sulfonate structure represented by the above formula (B1) is preferably a compound of the following formula (OS-3), the following formula (OS-4) or the following formula (OS). -5) The oxime sulfonate compound represented.

(In the general formula (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 are each independently The ground represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonate. The thiol group, X ¹ to X ³ each independently represents an oxygen atom or a sulfur atom, and n ¹ to n ³ each independently represent 1 or 2, and m ¹ to m ³ each independently represent an integer of 0 to 6.

In the above formula (OS-3) to formula (OS-5), the alkyl group, the aryl group or the heteroaryl group in R ²² , R ²⁵ and R ²⁸ may have a substituent.

In the above formula (OS-3) to formula (OS-5), the alkyl group in R ²² , R ²⁵ and R ²⁸ is preferably an alkyl group having a total carbon number of 1 to 30 which may have a substituent.

Further, in the above formula (OS-3) to formula (OS-5), the aryl group in R ²² , R ²⁵ and R ²⁸ is preferably an aryl group having a total carbon number of 6 to 30 which may have a substituent.

Further, in the above formula (OS-3) to formula (OS-5), the heteroaryl group in R ¹ is preferably a heteroaryl group having a total carbon number of 4 to 30 which may have a substituent.

In the above formula (OS-3) to formula (OS-5), the heteroaryl group in R ²² , R ²⁵ and R ²⁸ may be at least one ring which is a heteroaromatic ring, for example, a heteroaromatic ring and a benzene ring. Shrinkable ring.

In the above formula (OS-3) to formula (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.

In the above formula (OS-3) to formula (OS-5), two or more of R ²³ , R ²⁶ and R ²⁹ are present in the compound, and preferably one or two are alkyl groups, aryl groups or More preferably, one halogen atom is an alkyl group, an aryl group or a halogen atom, and particularly preferably one is an alkyl group, and the balance is a hydrogen atom.

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

The aryl group in R ²³ , R ²⁶ and R ²⁹ is preferably an aryl group having a total carbon number of 6 to 30 which may have a substituent.

In the above formula (OS-3) to formula (OS-5), X ¹ to X ³ each independently represent O or S, and is preferably O.

In the above formula (OS-3) to formula (OS-5), the ring containing X ¹ to X ³ as a ring member is preferably a 5-membered ring or a 6-membered ring.

In the above formula (OS-3) to formula (OS-5), n ¹ to n ³ each independently represent 1 or 2, and when X ¹ to X ³ are 0, n ¹ to n ^{3 are} preferred. In order to be independently 1, respectively, and in the case where X ¹ to X ³ are S, n ¹ to n ^{3 are} preferably independently 2 each.

In the above formula (OS-3) to formula (OS-5), R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or Alkoxysulfonyl. Wherein R ²⁴ , R ²⁷ and R ³⁰ are each independently an alkyl group or an alkoxy group.

The alkyl group, alkoxy group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group in R ²⁴ , R ²⁷ and R ³⁰ may have a substituent.

In the above formula (OS-3) to formula (OS-5), the alkyl group in R ²⁴ , R ²⁷ and R ³⁰ is preferably an alkyl group having a total carbon number of 1 to 30 which may have a substituent.

In the above formula (OS-3) to formula (OS-5), the alkoxy group in R ²⁴ , R ²⁷ and R ³⁰ is preferably an alkoxy group having a total carbon number of 1 to 30 which may have a substituent.

Further, in the above formula (OS-3) to formula (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. , especially good is 0.

Further, regarding each of the above formula (OS-3) to formula (OS-5) The preferred range of the substituent of (OS-3) to (OS-5) described in Paragraph No. 0092 to Paragraph No. 0109 of JP-A-2011-221494 is also preferable.

In addition, the compound containing the oxime sulfonate structure represented by the above formula (B1) is particularly preferably an oxime sulfonate represented by any one of the following formula (OS-6) to (OS-11). Compound.

(In the formula (OS-6)~(OS-11), R ³⁰¹ to R ³⁰⁶ represent an alkyl group, an aryl group or a heteroaryl group, and R ³⁰⁷ represents a hydrogen atom or a bromine atom, and R ³⁰⁸ to R ³¹⁰ and 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 ^R314 each independently represent a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ³¹² , R ³¹⁵ , R ³¹⁷ and R ³¹⁹ each independently represent a hydrogen atom or a methyl group.

Preferred range and date in the above formula (OS-6) to formula (OS-11) The preferred ranges of (OS-6) to (OS-11) described in Paragraph No. 0110 to Paragraph No. 0112 of Japanese Laid-Open Patent Publication No. 2011-221494 are also the same.

Specific examples of the oxime sulfonate compound represented by the above formula (OS-3) to the above formula (OS-5) include those described in paragraph No. 0114 to paragraph number 0120 of JP-A-2011-221494. A compound, but the invention is not limited to the compounds.

In the photosensitive resin composition of the present invention, the photo-acid generator is preferably used in an amount of 100 parts by mass based on the total resin component (preferably a solid component, more preferably a total of the copolymer) in the photosensitive resin composition. It is more preferably used in an amount of from 0.1 part by mass to 10 parts by mass, more preferably from 0.5 part by mass to 10 parts by mass. Two or more types 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. Since the alicyclic epoxy compound traps the acid generated by the acid generator quickly, it is considered that the photosensitive resin composition which is excellent in sensitivity, line width stability, resolution, and squareness is prepared by blending the compound.

The alicyclic epoxy group which the alicyclic epoxy compound used in the present invention is not particularly limited, and examples thereof include an alicyclic epoxy group directly added to a cyclic aliphatic hydrocarbon, and a cyclic fat. The hydrocarbon is preferably a 3-member ring to a 10-member ring, and more preferably a 5-member ring to a 6-member ring. Among them, an alicyclic epoxy group represented by the following is preferable.

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

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

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

The carbon number of the organic group of R ¹ is preferably from 1 to 8, more preferably from 1 to 6. The organic group is preferably a hydrocarbon group or a combination comprising at least one of a hydrocarbon group and a decyl group, -O-, -CO-, -S-, and -NR- (R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms). The group is more preferably a hydrocarbon group or a group containing a combination of a hydrocarbon group and -O- and/or -CO-. The hydrocarbon group is preferably a linear or branched group, more preferably a linear group. The carbon number of the hydrocarbon group is preferably from 1 to 4. One organic group may contain two or more hydrocarbon groups.

When the epoxy group in the alicyclic epoxy compound is ring-opened, when the acid is generated by the acid generator, the ring-opened epoxy group is bonded to the functional group of the polymer, and the alicyclic epoxy is lost. The case of the degree of freedom of the compound. Therefore, the amount of epoxy groups is higher Good for a small amount. n represents an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 1 or 2.

A preferred embodiment of the alicyclic epoxy compound is exemplified by the compound represented by the following formula (II).

(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, may be branched, may have an unsaturated bond, or may have a cyclic structure of an aliphatic ring or an aromatic ring. In addition, the groups may have oxygen, sulfur, nitrogen, phosphorus, boron, and halogen atoms. Further, it may have a substituent, and the substituents may form a bond with each other. Further, R ² is a divalent linking group.

The carbon number of the organic group of R ² is preferably from 1 to 8, more preferably from 1 to 6. The organic group is preferably a hydrocarbon group or a group containing a combination of a hydrocarbon group and at least one of -O-, -CO-, -S-, and -NR- (R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms). More preferably, it is a hydrocarbon group or a group containing a combination of a hydrocarbon group and -O- and/or -CO-. The hydrocarbon group is preferably a linear or branched group, more preferably a linear group. The carbon number of the hydrocarbon group is preferably from 1 to 4. Two or more hydrocarbon groups may be contained on one organic group. The hydrocarbon group is preferably an alkylene group.

A preferred embodiment of the alicyclic epoxy compound is also exemplified by the 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, may be branched, may have an unsaturated bond, or may have a cyclic structure of an aliphatic ring or an aromatic ring. In addition, the groups may have oxygen, sulfur, nitrogen, phosphorus, boron, and halogen atoms. Further, it may have a substituent, and the substituents may form a bond with each other. Further, R ³ is a divalent linking group.

The carbon number of the organic group of R ³ is preferably from 1 to 8, more preferably from 1 to 6. The organic group is preferably a hydrocarbon group or a group containing a combination of a hydrocarbon group and at least one of -O-, -CO-, -S-, and -NR- (R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms). More preferably, it is a hydrocarbon group or a group containing a combination of a hydrocarbon group and -O- and/or -CO-. The hydrocarbon group is preferably a linear or branched group, more preferably a linear group. The carbon number of the hydrocarbon group is preferably from 1 to 4. Two or more hydrocarbon groups may be contained on one organic group. The hydrocarbon group is preferably an alkylene group.

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

The alicyclic epoxy compound used in the present invention can be produced arbitrarily, for example, by referring to the following literature: "The Fourth Edition of Experimental Chemistry Lecture 20 Organic Synthesis II" by Maruzen KK, 213~, 1992; by Alfred The chemistry of heterocyclic compounds-Small Ring Heterocycles part3, edited by Hasfner Oxiranes)", John. John & Wiley and Sons, An Interscience Publication, New York, 1985; Yoshimura, "Next", Vol. 29, No. 12, p. 32, 1985; Yoshimura , "Continued", Vol. 30, No. 5, p. 42, 1986; Yoshimura, "Next", Vol. 30, No. 7, p. 42, 1986; Japanese Patent Laid-Open No. 1-100378, Japanese Patent No. 2906245 No., Japanese Patent No. 2924262, and the like.

The alicyclic epoxy compound used in the present invention has a molecular weight of less than 1,000, preferably less than 500. By setting it as the said range, the effect of this invention is exhibited more effectively. The lower limit is not particularly limited, but is usually 100 or more.

The amount of the alicyclic epoxy compound to be added to the photosensitive resin composition of the present invention is preferably 0.05 parts by mass to 5 parts by mass, more preferably 0.1% by mass, based on 100 parts by mass of the total solid content of the photosensitive resin composition. It is preferably 3 parts by mass, and more preferably 0.1 parts by mass to 1.5 parts by mass. The alicyclic epoxy compound may be used in combination, and in this case, the alicyclic epoxy compounds are all combined to calculate the content.

<(D) Solvent>

The photosensitive resin composition of the present invention contains (D1) a solvent containing two or more acetate structures in the molecule as (D) a solvent. The mechanism is not certain, but it is presumed to be a plasticizer which forms a moderate coating film by blending such a solvent, and is also moderately promoted by a quencher and an alicyclic epoxy compound. Capture acid to improve sensitivity, line width stability, resolution and rectangularity. The photosensitive resin composition of the present invention is preferably prepared by dissolving an essential component of the present invention and an optional component described later in (D1) a 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, and the number of acetate structures in the molecule is preferably two. 4, especially 2.

Further, the solvent containing two or more acetate structures in the molecule (D1) is preferably a solvent having a boiling point of 130 ° C or more and less than 300 ° C, preferably a solvent of 180 ° C or more and less than 270 ° C, more preferably 200 ° C. Above and less than 270 ° C solvent. Further, the boiling point means a boiling point at 1 atm unless otherwise specified. Further, when a solvent containing two or more kinds of solvents is mixed, the boiling point is obtained by weighting and averaging the boiling points of the respective solvents with respect to the total solvent by the respective weight ratios.

The solvent (D1) can be exemplified by 1,2-ethylene glycol diacetate, 1,2-propylene glycol diacetate, 1,3-propanediol diacetate, and 1,2-butanediol diacetic acid. Ester, 1,3-butanediol diacetate, 1,4-butanediol diacetate, 1,6-hexanediol diacetate, triacetin, and the like. (D1) The solvent 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 from 1% by mass to 10% by mass, particularly preferably from 1% by mass to 5% by mass, per 100 parts by mass of the photosensitive resin composition.

Further, in the solvent (D1), (D2) another solvent may be further added as needed to prepare a mixed solvent. In the case of the above mixed solvent, (D2) another solvent may be selected so that the respective solvents may be weighted and averaged with respect to the boiling point of the total solvent to obtain a temperature of 130 ° C or more and less than 300 ° C. (D2) The 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 ° C or more and less than 160 ° C and a solvent having a boiling point of 160 ° C or more, and specifically, propylene glycol monomethyl ether acetate (boiling point: 146 ° C), propylene glycol single a solvent containing one acetate structure in the molecule such as diethyl ether acetate (boiling point: 158 ° C); propylene glycol methyl-n-butyl ether (boiling point: 155 ° C), propylene glycol methyl-n-propyl ether (boiling point: 131 ° C) .

The solvent having a boiling point of 160 ° C or higher can be exemplified by ethyl 3-ethoxypropionate (boiling point: 170 ° C), diethylene glycol methyl ether (boiling point: 176 ° C), and propylene glycol monomethyl ether propionate (boiling point: 160 ° C), dipropylene glycol methyl ether acetate (boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), two Diol dimethyl ether (boiling point 162 ° C), diethylene glycol monoethyl ether acetate (boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C).

In addition to the above other solvents, a known solvent may be used, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, and 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, guanamines, lactones, and the like. In addition, as a specific example of the solvent (D2) used in the photosensitive resin composition of the present invention, the solvent described in Paragraph No. 0174 to Paragraph No. 0178 of JP-A-2011-221494 may be incorporated. In the specification of the present application.

In addition, it may be added as needed: benzyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, Caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, carbonic acid A solvent such as an ester or a propyl carbonate. 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 singly or in combination of two or more, more preferably two kinds, and particularly preferably propylene glycol monoalkyl ether acetate or dialkyl ether or diacetate. It is used in combination with diethylene glycol dialkyl ethers or esters and butanediol alkyl ether acetate.

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

<Other ingredients>

In addition to the above components, the photosensitive resin composition of the present invention may preferably contain (E) an alkoxydecane compound, (F) a crosslinking agent, (G) a sensitizer, and (H) a basic compound. (I) surfactant, (J) antioxidant. Further, an acid proliferating agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a tackifier, and an organic or inorganic precipitation preventable agent can be added to the photosensitive resin composition of the present invention. A known additive such as a agent.

(E) alkoxydecane compound

The photosensitive resin composition of the present invention is characterized by containing (E) an alkoxydecane compound (also referred to as "(E) component"). When an alkoxy decane compound is used, the adhesiveness of the film formed from the photosensitive resin composition of this invention and a board|substrate can be improved, or the film of the photosensitive resin composition of this invention can be adjusted. alkyl The oxydecane compound is preferably a dialkoxy decane compound or a trialkoxy decane compound, more preferably a trialkoxy decane compound. The alkoxy group of the alkoxydecane compound preferably has 1 to 5 carbon atoms.

The (E) alkoxydecane compound which can be used in the photosensitive resin composition of the present invention is preferably an inorganic substance which is a base material, for example, an antimony compound such as cerium, cerium oxide or cerium nitride, which improves gold, copper, molybdenum, and the like. A compound having adhesion to a metal such as titanium or aluminum and an insulating film. Specifically, a known decane coupling agent or the like is also effective.

Examples of the decane coupling agent include γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-glycidoxypropyltrialkoxydecane, and γ-glycidyloxy group. Propyl alkyl dialkoxy decane, γ-methyl propylene methoxy propyl trialkoxy decane, γ-methyl propylene methoxy propyl alkyl dialkoxy decane, γ-chloropropyl three Alkoxydecane, γ-mercaptopropyltrialkoxydecane, β-(3,4-epoxycyclohexyl)ethyltrialkoxydecane, vinyltrialkoxydecane. More preferably, these compounds are γ-glycidoxypropyltrialkoxydecane or γ-methacryloxypropyltrialkoxydecane, and particularly preferably γ-glycidoxypropyl III. The alkoxydecane, and more preferably 3-glycidoxypropyltrimethoxydecane. These compounds may be used alone or in combination of two or more.

Further, the following compounds can also be preferably used.

In the above, Ph is a phenyl group.

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

The content of the (E) alkoxydecane compound in the photosensitive resin composition of the present invention is preferably from 0.1 part by mass to 30 parts by mass, more preferably 0.5, based on 100 parts by mass of the total solid content of the photosensitive composition. Parts by mass to 20 parts by mass.

(F) crosslinker

The photosensitive resin composition of the present invention preferably contains a crosslinking agent as needed. The cured film obtained from the photosensitive resin composition of the present invention can be made into a stronger film by adding a crosslinking agent.

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

The amount of the crosslinking agent added to the photosensitive resin composition of the present invention is preferably from 0.01 part by mass to 50 parts by mass, more preferably from 0.1 part by mass to 30 parts by mass per 100 parts by mass of the total solid content of the photosensitive resin composition. The mass part is preferably from 0.5 part by mass to 20 parts by mass. By adding in this range, a cured film excellent in mechanical strength and solvent resistance is obtained. A plurality of crosslinking agents may be used in combination, and in this case, the total amount of the crosslinking agents is totaled to calculate the content.

<Compound 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 a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, and a cresol novolak type epoxy resin. Aliphatic epoxy resin, etc.

These compounds are available as commercial products. For example, a commercial item such as JER157S70 and JER157S65 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), paragraph number 0189 of JP-A-2011-221494.

In addition, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (above (made by ADEKA)), NC-2000, NC-3000, NC -7300, XD-1000, EPPN-501, EPPN-502 (made by ADEKA), Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX -521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX- 920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (above manufactured by Nagase ChemteX), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (above manufactured by Nippon Steel Chemical Co., Ltd.), Celloxide 2021P, 2081, 3000, EHPE3150, Epolead GT400, Celvenus B0134, B0177 (Daicel).

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

Among these compounds, preferred are bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, and aliphatic epoxy resins, and particularly preferred are bisphenol A type epoxy resins. Resin.

Specific examples of the compound having two or more oxetanyl groups in the molecule include Aron Oxetane OXT-121, OXT-221, OX-SQ, and PNOX (manufactured by Toagosei Co., Ltd.).

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

Further, other crosslinking agents may preferably be used: the alkoxymethyl group-containing crosslinking agent described in Paragraph No. 0107 to Paragraph No. 0108 of JP-A-2012-8223, and having at least one ethylene. Compounds of the unsaturated double bond, etc., are incorporated into the specification of the present application. The alkoxymethyl group-containing crosslinking agent is preferably an alkoxymethylated glycoluril.

<Block isocyanate compound>

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

Further, the term "block isocyanate group" in the present invention means a group which can form an isocyanate group by heat, and for example, it is preferably exemplified by reacting a block agent with an isocyanate group to protect Isocyanate group. Further, the block isocyanate group is preferably a group which can form an isocyanate group by heat of from 90 ° C to 250 ° C.

Further, the blocked isocyanate compound is not particularly limited as long as it has two isocyanato groups in one molecule, and is preferably an aliphatic, alicyclic or aromatic polyisocyanate, for example. It can be suitably used: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1, 4-tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene di Isocyanate, 1,10-decethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,2'-diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene Isocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis(cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-diene Diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-methylene xylene-4,4'-diisocyanate, 4,4'-diphenyl ether Diisocyanate, tetrachloro phenylene diisocyanate, norbornane diisocyanate An isocyanate compound such as an ester, hydrogenated 1,3-benzenedimethyl diisocyanate or hydrogenated 1,4-benzyldimethylisocyanate, and a compound of a prepolymer type skeleton derived from the compounds. Among these compounds, particularly preferred is tolylene diisocyanate (TDI) or diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate. (isophorone diisocyanate, IPDI).

The parent structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention may be a biuret type, an isocyanurate type, an adduct type or a bifunctional type. Polymer type, etc.

Examples of the block forming the block structure of the above-mentioned blocked isocyanate compound include an anthracene compound, an indoleamine compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a thiol compound, and an imidazole system. a compound, a quinone imine compound, or the like. Among these compounds, a block agent selected from the group consisting of an anthracene compound, an indoleamine compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, and a pyrazole compound is particularly preferred.

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

The above-mentioned indoleamine compound can be exemplified by ε-caprolactam, γ-butylide or the like.

The phenol compound may, for example, be phenol, naphthol, cresol, xylenol or halogen-substituted phenol.

The above alcohol compounds can be exemplified by methanol, ethanol, propanol, butanol, and cyclohexane. Alcohol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, alkyl lactate, and the like.

Examples of the amine compound include a primary amine and a secondary amine, and may be any of an aromatic amine, an aliphatic amine, and an alicyclic amine, and examples thereof include aniline, diphenylamine, ethylenimine, and polycondensation. Ethyl imine and the like.

The active methylene compound may, for example, be diethyl malonate, dimethyl malonate, ethyl acetate or ethyl acetate.

The above pyrazole compound can be exemplified by pyrazole, methylpyrazole, dimethylpyrazole and the like.

The above thiol compound can be exemplified by an alkylthiol, an arylthiol or the like.

The blocked isocyanate compound which can be used in the photosensitive resin composition of the present invention can be obtained as a commercial product, and for example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS- can be preferably used. 50 (above manufactured by Nippon Polyurethane Industry), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (The above is manufactured by Mitsui Chemicals Co., Ltd.), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN- 70D, SBB-70P, K6000 (above manufactured by Asahi Kasei Chemicals), Desmodur BL1100, BL1265 MPA/X, BL3575/1, BL3272MPA, BL3370MPA, BL3475BA/SN, BL5375MPA, VPLS2078/2, BL4265SN , PL340, PL350, Sumidur BL3175 (above, manufactured by Sumika Bayer Urethane).

(G) sensitizer

In combination with the (B) photoacid generator, the photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote decomposition thereof. The sensitizer absorbs actinic rays or radiation and becomes an electronically excited state. The sensitizer that is in an electronically excited state is brought into contact with the photoacid generator to cause electron transfer, energy transfer, heat generation, and the like. Thereby, the photoacid generator generates a chemical change to decompose to form an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength at any wavelength in the wavelength region of 350 nm to 450 nm.

Polynuclear aromatics (eg, ruthenium, osmium, extended triphenyl, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10 -dipropoxy fluorene), xanthene (eg fluorescein, eosin, erythrosine, rhodamine B, bengal rose red) Rose bengal)), xanthone (eg xanthonone, thioxanthone, dimethyl thiazolone, dithionone), cyanine (eg, thiacarbocyanine, oxacarbocyanine, merocyanine) (eg, merocyanine, carbomerocyanine), rhodacyanine ), oxonols, thiazines (eg, thionine, methylene blue, toluidine blue), acridine (acridine) For example: acridine orange, chloroflavin, acriflavine, acridone (eg acridone, 10-butyl-2-chloroacridine) Ketone, 10-butyl acridone), hydrazine (anthraquinone) (eg 蒽醌), squaraine compounds (eg squaraine compounds), styryls, basic styryls (eg 2-[2-[4-(dimethylamine) Phenyl]vinyl]benzoxazole), coumarin (eg 7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin) 2,3,6,7-tetrahydro-9-methyl-1H,5H,11H[1]benzopyrano[6,7,8-ij]quinolizin-11-one).

Among these sensitizers, polynuclear aromatics, acridones, styrenes, basic styrenes, and coumarins are preferred, and polynuclear aromatics are more preferred. Among the polynuclear aromatics, the most preferred is an anthracene derivative.

The amount of the sensitizer added to the photosensitive resin composition of the present invention is preferably from 0 part by mass to 1000 parts by mass, more preferably 10 parts by mass, based on 100 parts by mass of the photoacid generator of the photosensitive resin composition. 500 parts by mass, particularly preferably 50 parts by mass to 200 parts by mass.

Two or more types may be used in combination.

(H) basic compound

The photosensitive resin composition of the present invention may contain (H) a basic compound. (H) The basic compound can be arbitrarily selected from the users of the chemical amplification resist to be used. For example, an aliphatic amine, an aromatic amine, a heterocyclic amine, a quaternary ammonium hydroxide, a quaternary ammonium salt of a carboxylic acid, etc. are mentioned. Specific examples of such a compound include the compounds described in Paragraph No. 0204 to Paragraph No. 0207 of JP-A-2011-221494, the contents of which are incorporated herein by reference. Further, thioureas such as N-cyclohexyl-N'-[2-(4-morpholinyl)ethyl]thiourea can also be used.

The basic compound which can be used in the present invention may be used alone or in combination. Two or more types are used together.

In the case where the other basic compound is contained, the content of the (H) other basic compound in the photosensitive resin composition of the present invention is preferably 0.001 by mass based on 100 parts by mass of the total solid content in the photosensitive resin composition. It is preferably 3 parts by mass, more preferably 0.005 parts by mass to 1 part by mass.

(I) surfactant

The photosensitive resin composition of the present invention may contain (I) a surfactant. (I) The surfactant may be any of an anionic, cationic, nonionic or amphoteric surfactant, and a preferred surfactant is a nonionic surfactant.

Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, anthrone series, and fluorine-based interfacial activity. Agent. In addition, the following product names are listed: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), Eftop (manufactured by JEMCO), and Megafac (DIC). () manufacturing), Fluorad (Sumitomo 3M (share) manufacturing), Asahi Guard, Surflon (made by Asahi Glass Co., Ltd.), PolyFox (made by OMNOVA), SH-8400 (Toray Dow Corning (Toray) Dow Corning Silicone)) and other series.

Further, the surfactant is preferably a copolymer comprising a constituent unit A represented by the following formula (I-1) and a constituent unit B, and using tetrahydrofuran (THF) as a solvent. The polystyrene-equivalent weight average molecular weight (Mw) measured by the gel permeation chromatography in the case is 1,000 or more and 10,000 or less.

(In the formula (I-1), R ⁴⁰¹ and R ⁴⁰³ each represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 or more and 4 or less carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or a carbon number of 1 or more. 4 or less alkyl groups, L represents an alkylene group having 3 or more and 6 or less carbon atoms, p and q are mass percentages indicating a polymerization ratio, p is a numerical value of 10% by mass or more and 80% by mass or less, and q is 20% by mass. The above numerical value of 90% by 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.)

The above L is preferably a branched alkyl group represented by the following formula (I-2). R ⁴⁰⁵ in the formula (I-2) represents an alkyl group having 1 or more and 4 or less carbon atoms, and preferably has a carbon number of 1 or more and 3 in terms of compatibility and wettability to a surface to be coated. The alkyl group below is more preferably an alkyl group having 2 or 3 carbon atoms. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by mass.

General formula (I-2)

The weight average molecular weight (Mw) of the above copolymer is more preferably 1,500 or more and 5,000 or less.

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

The amount of the (I) surfactant 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, based on 100 parts by mass of the total solid content in the photosensitive resin composition. 10 parts by mass, particularly preferably 0.01 parts by mass to 3 parts by mass.

(J) Antioxidants

The photosensitive resin composition of the present invention may contain an antioxidant. The antioxidant may contain a well-known antioxidant. By adding an antioxidant, it is possible to prevent the coloration of the cured film, or to reduce the film thickness caused by decomposition, and to have an advantage of excellent heat-resistant transparency.

Examples of the antioxidant as described above include phosphorus-based antioxidants, guanamines, guanidines, hindered amine-based antioxidants, sulfur-based antioxidants, phenolic antioxidants, ascorbic acid, zinc sulfate, saccharides, and nitrites. , sulfites, thiosulfates, hydroxylamine derivatives, and the like. Among these compounds, a phenolic antioxidant, a guanamine antioxidant, a lanthanoid antioxidant, and a sulfur-based antioxidant are particularly preferable from the viewpoint of coloring and film thickness reduction of the cured film. These compounds may be used alone or in combination of two. Mix above.

Commercial products of phenolic antioxidants include, for example, Adekastab AO-15, Adekastab AO-18, Adekastab AO-20, Adekastab AO-23, Adekastab AO-30, Adekastab AO-37, Adekastab AO-40, Adekastab AO- 50. Adekastab AO-51, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-330, Adekastab AO-412S, Adekastab AO-503, Adekastab A-611, Adekastab A-612, Adekastab A- 613, Adekastab PEP-4C, Adekastab PEP-8, Adekastab PEP-8W, Adekastab PEP-24G, Adekastab PEP-36, Adekastab PEP-36Z, Adekastab HP-10, Adekastab 2112, Adekastab 260, Adekastab 522A, Adekastab 1178, Adekastab 1500, Adekastab C, Adekastab 135A, Adekastab 3010, Adekastab TPP, Adekastab CDA-1, Adekastab CDA-6, Adekastab ZS-27, Adekastab ZS-90, Adekastab ZS-91 (above manufactured by ADEKA), Irganox 245FF Irganox 1010FF, Irganox 1010, Irganox MD1024, Irganox 1035FF, Irganox 1035, Irganox 1098, Irganox 1330, Irganox 1520L, Irganox 3114, Irganox 1726, Irgafos 168, Irgamod 295 (manufactured by BASF). Among them, Adekastab AO-60, Adekastab AO-80, Irganox 1726, Irganox 1035, Irganox 1098 can be suitably used.

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

In addition, as the additive other than the antioxidant, various ultraviolet absorbers, metal passivators, and the like described in "New Development of Polymer Additives" (Nikkei Kogyo Co., Ltd.) may be added to the photosensitive resin of the present invention. In the composition.

[acid proliferator]

The photosensitive resin composition of the present invention can use an acid multiplier for the purpose of improving sensitivity.

The acid multiplying agent which can be used in the present invention is a compound which can further generate an acid by an acid catalyst reaction and raise the acid concentration in the reaction system, and is a compound which is stably present in the absence of an acid. Since such a compound is increased by one or more acids by one reaction, the reaction proceeds with the progress of the reaction, but since the generated acid itself causes self-decomposition, the strength of the acid generated here is dissociated by acid. The constant and pKa are preferably 3 or less, and particularly preferably 2 or less.

Specific examples of the acid-proliferating agent include paragraph number 0203 to paragraph number 0223 of JP-A-10-1508, paragraph number 0016 to paragraph number 0055 of Japanese Patent Laid-Open No. Hei 10-282642, and Japanese Patent Special Table. The compounds described in Japanese Patent Publication No. Hei 9-512498, page 39, line 12 to page 47, line 2, are incorporated herein by reference.

The acid multiplying agent which can be used in the present invention is decomposed by using an acid generated by an acid generator to produce dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, phenylphosphonic acid, or the like. A compound having an acid having a pKa of 3 or less.

Specifically, it can be enumerated: Wait.

The content of the acid-proliferating agent in the photosensitive composition is preferably from 10 parts by mass to 1,000 parts by mass, based on 100 parts by mass of the photo-acid generator, from the viewpoint of the dissolution ratio of the exposed portion and the unexposed portion. The optimum is set to 20 parts by mass to 500 parts by mass.

[development accelerator]

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

The development accelerator can be referred to the description of Paragraph No. 0171 to Paragraph No. 0172 of Japanese Patent Laid-Open No. 2012-042837, which is incorporated herein by reference.

One type of the development accelerator may be used alone or two or more types may be used in combination.

From the viewpoint of the sensitivity and the residual film ratio, the amount of the development accelerator added to the photosensitive resin composition of the present invention is preferably from 0 to 30 mass% per 100 parts by mass of the total solid content of the photosensitive composition. The portion is more preferably 0.1 part by mass to 20 parts by mass, most preferably 0.5 part by mass to 10 parts by mass.

Further, other additives may be produced by using the thermal radicals described in paragraph number 0120 to paragraph 0121 of JP-A-2012-8223. The nitrogen-containing compound and the thermal acid generator described in WO2011/136074A1 are incorporated herein by reference.

<Method for Preparing Photosensitive Resin Composition>

The components are mixed at a predetermined ratio and by any method, and stirred and dissolved to prepare a photosensitive resin composition. For example, after the components are each dissolved in a solvent to prepare a solution, the solutions are mixed at a predetermined ratio to prepare a resin composition. The composition solution prepared in the above manner can also be filtered by using a filter having a pore size of 0.2 μm or the like, and then used.

[Method of manufacturing pattern]

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

The method for producing a 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) a step of removing a solvent from the applied photosensitive resin composition; and (3) removing a solvent by an actinic ray pair a step of exposing the photosensitive resin composition; (4) a step of developing the exposed photosensitive resin composition with an aqueous developing solution; and (5) using the formed resist pattern as a mask for the above The step of etching the substrate.

Each step will be described in order below.

In the coating step of (1), the photosensitive resin group of the present invention is preferably used. The product is coated on a substrate to form a wet film containing a solvent. It is preferred to perform cleaning of the substrate such as alkali cleaning or plasma cleaning before applying the photosensitive resin composition onto the substrate, and it is more preferable to treat the surface of the substrate with hexamethyldiazepine after the substrate cleaning. By performing 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 hexamethyldioxane is not particularly limited, and examples thereof include a method of exposing a substrate to hexamethyldioxane vapor.

Examples of the substrate include an inorganic substrate, a resin, and a resin composite material. For example, a chromium film, a molybdenum film, a molybdenum alloy film, a ruthenium film, a ruthenium alloy film, an indium oxide (ITO) film doped with tin oxide, or tin oxide can be used. Metal substrate such as film, Ni, Cu, Fe, Al, etc.; quartz, glass, tantalum nitride film, anthrone, fluorenone, fluorenone, fluorenone, amorphous fluorenone film, spin-on glass (Spin -On-Glass, SOG), germanium wafers for semiconductor device manufacturing, and germanium substrates such as glass substrates for liquid crystal element manufacturing; paper, polyester film, polycarbonate film, polyimide film, and organic EL display device A polymer substrate such as another polymer substrate used; a ceramic material, a Ti substrate, an Al substrate, or the like. In the present invention, an ITO substrate, a molybdenum substrate, a tantalum substrate, a Cu substrate, or an Al substrate is preferable, and an ITO substrate, a molybdenum substrate or a tantalum substrate is more preferable, and an ITO substrate is particularly preferable.

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

The method of applying the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a cast coating method, a slit, and a spin method (slit-and- Spin method) and other methods. Further, a so-called pre-wet method described in Japanese Laid-Open Patent Publication No. 2009-145395 can also be applied.

The wet film thickness at the time of application is not particularly limited, and it can be applied in a film thickness suitable for the application, and is usually used in the range of 0.5 μm to 10 μm.

In the solvent removal step of (2), a solvent is removed from the applied film by pressure reduction (vacuum) and/or heating to form a dried coating film on the substrate. The heating condition in the solvent removal step is preferably from 70 ° C to 130 ° C and from about 30 seconds to 300 seconds. When the temperature and time are in the above range, the adhesion of the pattern is further improved, and the residue tends to be further reduced.

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

The exposure light source by actinic ray can be used: a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generating device, etc., which can be preferably used. An actinic ray having a wavelength of 300 nm or more and 450 nm or less, such as g-ray (436 nm), i-ray (365 nm), and h-ray (405 nm). Further, the illumination light may be adjusted by a long-wavelength cut filter, a short-wavelength cut filter, or a band pass filter such as a band pass filter as needed.

The exposure device can be used: a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, Various types of exposure machines such as laser exposure.

In the region where the acid catalyst is formed, in order to accelerate the hydrolysis reaction, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as "PEB") may be performed. By PEB, it is possible to promote the formation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The temperature in the case of performing PEB is preferably 30° C. or higher and 130° C. or lower, more preferably 40° C. or higher and 110° C. or lower, and particularly preferably 50° C. or higher and 100° C. or lower.

In particular, the acid-decomposable group in the present invention has a low activation energy due to acid decomposition, and is easily decomposed by an acid derived from an acid generator generated by exposure to produce a carboxyl group or a phenolic hydroxyl group, so that it is not necessary to carry out PEB. A positive image is formed by development.

The developer used in the step (4) preferably contains a basic compound. As the basic compound, for example, an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide; an alkali metal carbonate such as sodium carbonate or potassium carbonate; or an alkali metal hydrogencarbonate such as sodium hydrogencarbonate or potassium hydrogencarbonate; Salt; ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or choline hydroxide; aqueous solution of sodium citrate or sodium metasilicate. Further, an aqueous solution of an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the aqueous solution of the above-mentioned alkali as a developing solution.

The pH of the developer is preferably from 10.0 to 14.0.

The development time is preferably from 30 seconds to 180 seconds, and the development method may be any one of a puddle method and a dipping method. After development, a running water wash can be performed for 30 seconds to 90 seconds to form a desired pattern.

In the step (5), the method of etching the substrate by 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 further comprise (6) a step of peeling off the resist pattern. The method of peeling off the resist pattern is not particularly limited, and a known method can be used. Alternatively, the resist pattern can be removed by plasma treatment or chemical treatment.

[hardened film]

In the present invention, after the step of developing (4), the pattern corresponding to the unexposed area obtained by development is subjected to a predetermined temperature, for example, 180 ° C to 250 ° C using a heating means such as a hot plate or an oven. The heat treatment for the time is, for example, a heat treatment for 5 minutes to 60 minutes on a hot plate, and a heat treatment for 30 minutes to 90 minutes in the case of an oven, whereby a protective film excellent in heat resistance and hardness can be formed. A cured film such as an interlayer insulating film.

Further, when the heat treatment is performed, the transparency of the cured film can be improved by performing in a nitrogen atmosphere.

Further, it is preferred that the substrate on which the cured film is formed into a pattern is re-exposed by actinic rays before the heat treatment, and then heated.

That is, in order to form the cured film of the present invention, it is preferred to include a step of performing re-exposure with actinic rays between the step of developing and the step of thermally hardening.

The exposure in the step of re-exposure may be carried out by the same means as the above-described exposure step, and in the step of re-exposure, it is preferred to perform overall exposure on the side of the substrate on which the film of the photosensitive resin composition of the present invention is formed. A preferred exposure amount for the step of re-exposure is from 100 mJ/cm ² to 1,000 mJ/cm ² .

[pattern]

The pattern of the present invention is a pattern obtained by etching a substrate by using a resist pattern obtained by curing the photosensitive resin composition of the present invention as a mask. The pattern of the present invention is preferably used as an ITO pattern, a molybdenum pattern or a ruthenium pattern, and more preferably as an ITO pattern.

Since the photosensitive resin composition of the present invention is excellent in sensitivity, resolution, and exposure latitude, a resist pattern having excellent squareness is obtained. Since the pattern of the present invention is obtained by the pattern manufacturing method of the present invention using the above-described resist pattern, fine processing can be performed, and the organic EL display device or the liquid crystal display device can have high-definition display characteristics.

[Liquid Crystal Display Device]

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

The liquid crystal display device of the present invention is not particularly limited as long as it has a planarizing film or an interlayer insulating film formed using the photosensitive resin composition of the present invention, and a known liquid crystal display device having various structures can be cited.

Specific examples of the thin film transistor (TFT) included in the liquid crystal display device of the present invention include amorphous germanium-TFT, low-temperature polysilicon-TFT, and oxide semiconductor TFT. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.

In addition, the liquid crystal display method that can be adopted by the liquid crystal display device of the present invention can be Listed: Twisted Nematic (TN), Vertical Alignment (VA), In-Place-Switching (IPS), Frings Field Switching (FFS), Optical The Optical Compensated Bend (OCB) method.

In the panel structure, the cured film of the present invention can also be used in a color filter on Allay (COA) type liquid crystal display device, for example, as an organic insulating film of Japanese Laid-Open Patent Publication No. 2005-284291 ( 115) or an organic insulating film (212) of JP-A-2005-346054.

Moreover, the specific alignment of the liquid crystal alignment film which can be taken by the liquid crystal display device of the present invention may be, for example, a rubbing alignment method or a photoalignment method. In addition, the polymer can be supported by the polymer by the Polymer Sustained Alignment (PSA) technique described in JP-A-2003-149647 or JP-A-2011-257734.

Further, the photosensitive resin composition of the present invention and the cured film of the present invention are not limited to the above applications, and can be used for various purposes. For example, in addition to the planarization film or the interlayer insulating film, it may be suitably used for a protective film of a color filter or a spacer for maintaining a constant thickness of a liquid crystal layer in a liquid crystal display device or in a solid imaging element. A microlens or the like provided on a color filter.

FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel is provided with an element of the TFT 16, and the elements of the TFT 16 are disposed on two glass substrates 14 and a glass substrate 15 to which a polarizing film is attached. Room There is a pixel correspondence. On each element formed on the glass substrate, an ITO transparent electrode 19 on which a pixel electrode is formed is wired through a contact hole 18 formed in the cured film 17. A layer of the liquid crystal 20 and a red green blue (RGB) color filter 22 in which a black matrix is disposed are disposed on the ITO transparent electrode 19.

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

In addition, the liquid crystal display device can also be made into a three-dimensional (3D) (stereoscopic) type device or a touch panel type device. Further, it can be made into a flexible type, and can be used as the second interphase insulating film (48) of JP-A-2011-145686 or the interphase insulating film (520) of JP-A-2009-258758.

[Organic EL display device]

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

The organic EL display device of the present invention is not particularly limited as long as it has a planarizing film or an interlayer insulating film formed by using the photosensitive resin composition of the present invention, and various known organic EL display devices having various structures or Liquid crystal display device.

Specific examples of the thin film transistor (TFT) included in the organic EL display device of the present invention include amorphous germanium-TFT, low-temperature polysilicon-TFT, and oxide semiconductor TFT. The cured film of the present invention is electrically The characteristics are excellent, and thus can be combined in the TFTs and used preferably.

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

A bottom gate type TFT 1 is formed on the glass substrate 6 to cover the TFT 1 to form an insulating film 3 containing Si ₃ N ₄ . After the contact hole (not shown) is formed on the insulating film 3, the wiring 2 (having a height of 1.0 μm) connected to the TFT 1 is formed on the insulating film 3 via the contact hole. The wiring 2 is for connecting the organic EL element formed between the TFTs 1 or in the step described later to the TFT 1.

Further, in order to planarize the unevenness due to the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state in which the unevenness caused by the wiring 2 is buried.

A bottom emission type organic EL element is formed on the planarization film 4. That is, on the planarizing film 4, the first electrode 5 including ITO is formed by being connected to the wiring 2 via the contact hole 7. Further, the first electrode 5 corresponds to the anode of the organic EL element.

The insulating film 8 having a shape covering the periphery of the first electrode 5 is formed, and by providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent step can be prevented.

Further, in FIG. 2, a hole transport layer, an organic light-emitting layer, and an electron transport layer are sequentially deposited by interposing a desired pattern mask, and then a second layer containing Al is formed on the entire upper surface of the substrate. The electrode is bonded to the glass plate for sealing by using an ultraviolet curable epoxy resin, and an active matrix organic EL display device in which the TFT 1 for driving the organic EL element is connected to the organic EL element is obtained.

Since the photosensitive resin composition of the present invention is excellent in curability and cured film characteristics, a resist pattern formed using the photosensitive resin composition of the present invention as a structural member of a microelectromechanical system (MEMS) device is used. It is made into a partition or assembled as part of a mechanically driven part. Examples of such a MEMS element include a surface acoustic wave (SAW) filter, a bulk acoustic wave (BAW) filter, a gyro sensor, and a microshutter for display. , image sensor, electronic paper, inkjet head, biochip, sealant and other parts. More specific examples are exemplified in JP-A-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.

The photosensitive resin composition of the present invention is excellent in flatness and transparency, and can be used to form a bank layer (16) and a planarizing film as shown in Fig. 2 of JP-A-2011-107476. (57), the partition wall (12) and the flattening film (102) described in Fig. 4 (a) of Japanese Patent Laid-Open Publication No. 2010-9793, and the stacking shown in Fig. 10 of Japanese Patent Laid-Open Publication No. 2010-27591 The layer (221) and the third interlayer insulating film (216b), the second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4(a) of JP-A-2009-128577, The planarizing film (12) and the pixel separation insulating film (14) described in Fig. 3 of Japanese Laid-Open Patent Publication No. 2010-182638.

Example

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

In the following synthesis examples, the following symbols represent the following compounds, respectively.

MAEVE: 1-ethoxyethyl methacrylate

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

PHS: p-hydroxystyrene

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 distilled under reduced pressure, and water and PGMEA were removed by azeotropic distillation. After confirming that the water content 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. The reaction was stopped by adding 0.28 g of triethylamine thereto. Ethyl acetate was added to the reaction liquid, and after washing with water, the PGMEA of ethyl acetate, water, and azeotropic component was distilled off by distillation under reduced pressure to obtain an alkali-soluble resin which is protected by an acid-decomposable group. Polymer 1. The weight average molecular weight of the obtained resin was 11,000. In addition, the polydispersity was 1.13.

The structure of polymer 1 is a 1-ethoxyethyl protecting body 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 carry out azeotropic distillation of water and PGMEA. . After confirming that the water content 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. The reaction was stopped by adding 0.090 g of triethylamine thereto. Ethyl acetate was added to the reaction liquid, and the mixture was washed with water, and then distilled under reduced pressure to distill ethyl acetate and water to obtain a polymer 2 as a soluble resin having a protection ratio of 25 mol%. The obtained resin had a weight average molecular weight of 12,000. In addition, the polydispersity was 1.13.

The structure of the polymer 2 was a 2-tetrahydrofuran-protected/p-hydroxystyrene copolymer (30 mol% / 70 mol%) of p-hydroxystyrene.

Polymer 2

<Synthesis of Polymer 3>

The polymer 3 was synthesized in the following manner.

0.5 parts of phenothiazine was added to 144.2 parts (2 moles equivalent) of ethyl vinyl ether, and 86.1 parts of methacrylic acid (1 molar equivalent) was added dropwise while cooling to 10 ° C or lower in the reaction system, and then at room temperature. Stir at (25 ° 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 liquid, and the mixture was stirred at room temperature for 1 hour, and the insoluble matter was filtered, and concentrated under reduced pressure at 40 ° C or less to obtain a yellow oil of the residue. 134.0 parts of 1-ethoxyethyl methacrylate (MAEVE) having a boiling point (bp.) of 43 ° C / 7 mmHg - 45 ° C / 7 mmHg fraction was used as a colorless oil.

The resulting 1-ethoxyethyl methacrylate (63.28 parts (0.4 mole equivalent)), BzMA (52.83 parts (0.3 mole equivalent)), MAA (8.61 parts (0.1 mole equivalent)), HEMA ( A mixed solution of 26.03 parts (0.2 mole equivalent) and EDM (110.8 parts) was heated to 70 ° C under a nitrogen stream. While stirring the mixed solution, a mixed solution of a 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 the completion of the dropwise addition, the reaction was carried out at 70 ° C for 4 hours, thereby obtaining an EDM solution of the polymer. Liquid (solid content concentration: 40%).

The weight average molecular weight of the obtained polymer 3 as measured by Gel Permeation Chromatography (GPC) was 15,000.

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

(photoacid generator)

PAG-1: It is synthesized according to the method described in paragraph 0108 of JP-A-2002-528451.

The Ts portion represents a tosyl group.

(alicyclic epoxy compound)

C1: The following compound (manufacturer: manufactured by Daicel Chemical Industry Co., Ltd., product number: Celloxide 2021P)

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

C3: The following compound (manufacturer: manufactured by Daicel Chemical Industry Co., Ltd., product number: Celloxide 2081)

C4: The following compound (manufacturer: manufactured by Daicel Chemical Industry Co., Ltd., product number: Epolead GT-401)

C5: 157865 (manufacturer: manufactured by Mitsubishi Chemical Corporation)

C6: The following compound (manufactured by Changchun Chemical Co., Ltd., product number: EX-321L)

(solvent)

PGMEA: methoxypropyl acetate (manufactured by Showa Denko)

PGDA: 1,2-propanediol diacetate (boiling point 190 ° C, manufacturer: manufactured by Daicel Co., Ltd., product number: PGDA)

1,3-BGDA: 1,3-butylene glycol diacetate (boiling point: 232 ° C, manufacturer: manufactured by Daicel Co., Ltd., product number: 1,3-BGDA)

1,6-HDDA: 1,6-hexanediol diacetate (boiling point: 260 ° C, manufacturer: manufactured by Daicel Co., Ltd., product number: 1,6-HDDA)

DRA-150: Triacetin (boiling point 260 ° C, manufacturer: big game Manufactured by Ltd., product code: DRA-150)

DPNB: dipropylene glycol-n-butyl ether (boiling point: 229 ° C, manufacturer: manufactured by Daicel Co., Ltd., product number: DPNB)

BDGAC: Diethylene glycol monobutyl ether acetate (boiling point: 247 ° C, manufacturer: manufactured by Daicel Co., Ltd., product number: DPNB)

(sensitizer)

G-1 (manufacturer: Kawasaki Chemical Industrial Co., Ltd., product number: 9,10-dibutoxy oxime)

(alkaline compound)

H-1: (manufacturer: Toyo Chemical Co., Ltd., product number: CMTU)

(Preparation of photosensitive resin composition)

The components were dissolved and mixed in a manner shown in the following table, and filtered through a filter made of polytetrafluoroethylene having a diameter of 0.2 μm to obtain photosensitive resin compositions of the examples and the comparative examples. In addition, the deployment is as described in the following table.

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

. (B) Photoacid generator 3.0% by weight based on 100 parts by weight of the (A) polymer

. The alicyclic epoxy compound was formulated in an amount as described in the following table with respect to 100 parts by weight of the (A) polymer.

. (D1) Solvent The amount as described in the following table was adjusted with respect to the total solvent.

. (D2) Solvent The solvent was prepared so that the nonvolatile content was 20% by weight based on the composition.

. The basic compound is 0.2% by weight based on 100 parts by weight of the (A) polymer

. The sensitizer is 3.0% by weight based on 100 parts by weight of the (A) polymer

Each of the photosensitive resin compositions of the respective examples and comparative examples obtained as described above was subjected to the following evaluations.

<Evaluation of sensitivity>

The film was applied to a glass substrate treated with hexamethyldisilazane (HMDS) at a film thickness of 1.3 μm, and exposed and developed through a mask to form a 10 μm line and space pattern of 10 μm. The amount is evaluated as the optimum exposure amount. 3 or more is a practical level.

1: Requires exposure of 100mJ/cm ² or more

2: An exposure amount of 50 mJ/cm ² or more and less than 100 mJ/cm ² is required

3: An exposure amount of 20 mJ/cm ² or more and less than 50 mJ/cm ² is required

4: 10 mJ/cm ² or more and less than 20 mJ/cm ² of exposure

5: Exposure amount less than 10 mJ/cm ²

<Evaluation of line width stability>

The film was applied to a cleaned, HMDS-treated glass substrate at a film thickness of 1.3 μm, and exposed and developed with an exposure amount of 10 μm in a line and space pattern of 10 μm through a mask to prepare 10 lines with the line. With a space-patterned substrate, an optical measuring device ZYGO New View 7200 (manufactured by ZYGO Corp.) was used to measure a line width of 10 μm for 10 points on each substrate, and a total line width of 100 points was calculated. Standard deviation (σ). The evaluation criteria are as follows, and 3 or more is a practical level.

1: Standard deviation σ is 0.4 μm or more

2: The standard deviation σ is 0.2 μm or more and less than 0.4 μm

3: The standard deviation σ is 0.15 μm or more and less than 0.25 μm

4: The standard deviation σ is 0.1 μm or more and less than 0.15 μm

5: Standard deviation σ is less than 0.1 μm

<Evaluation of resolution>

The film thickness of 1.3 μm was applied to the cleaned, HMDS-treated glass substrate, and exposed and developed through a mask, and the minimum pattern that can be analyzed in the line and space pattern was used as the resolution. 3 or more is a practical level.

1: Resolution is 5 μm or more

2: 3.0 μm for analysis, and 2.5 μm for unresolved

3: 2.5 μm for analysis, and 2.0 μm for unresolved

4: 2.0 μm for analysis, and 1.5 μm for unresolved

5: 1.5 μm for analysis.

<Evaluation of Rectangularity>

The film was applied to a cleaned, HMDS-treated glass substrate at a film thickness of 1.3 μm, exposed and developed with a line and space pattern of 10 μm in an amount of 10 μm across the mask, and heated using the formed substrate. The plate was post-baked at a temperature of 140 ° C for 3 minutes (Post Bake), and the taper angle of the L·S pixel of 3 μm was measured and taken as a rectangular shape. 3 or more is a practical level.

1: cone angle is less than 30°

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

3: The taper angle is 45° or more and less than 60°

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

5: The taper angle is 75° or more

As shown in the above-mentioned table, the photosensitive resin composition of each of the examples was excellent in evaluation of any of sensitivity, resolution, and rectangularity in comparison with the photosensitive resin composition of each comparative example. the result of.

(Embodiment 16)

<Organic EL display device>

An organic EL display device having an ITO pattern (see FIG. 1) was produced by the following method.

A bottom gate type TFT 1 is formed on the glass substrate 6 to cover the TFT 1 to form an insulating film 3 containing Si ₃ N ₄ . Then, a contact hole (not shown) is formed on the insulating film 3, and then a wiring 2 (having a height of 1.0 μm) connected to the TFT 1 is formed on the insulating film 3 via the contact hole. This wiring 2 is for connecting the organic EL element formed between the TFTs 1 or in the step described later to the TFT 1.

Further, in order to planarize the unevenness due to the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state in which the unevenness caused by the wiring 2 is buried. The planarization film 4 is formed on the insulating film 3, and the photosensitive resin composition described in the first embodiment of JP-A-2009-98616 is spin-coated on a substrate, and pre-baked on a hot plate ( After 90 ° C × 2 minutes), an i-ray (365 nm) of 45 mJ/cm ² (illuminance: 20 mW/cm ² ) was irradiated from a mask using a high-pressure mercury lamp, and then developed by an aqueous alkali solution to form a pattern at 230 ° C. Heat treatment was carried out for 60 minutes.

When the photosensitive resin composition was applied, the coating property was good, and no occurrence of wrinkles or cracks was observed on the cured film obtained after exposure, development, and firing. Further The average step of the line 2 was 500 nm, and the film thickness of the produced planarizing film 4 was 2,000 nm.

Then, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, the first electrode 5 including ITO is connected to the wiring 2 via the contact hole 7 on the planarizing film 4. Then, the photosensitive resin composition of Example 1 was spin-coated on an ITO substrate, prebaked on a hot plate (90 ° C × 2 minutes), and then irradiated with a high-pressure mercury lamp to cover 20 mJ/cm from the mask. After i-ray (365 nm) of ² (illuminance: 20 mW/cm ² ), development was carried out using an aqueous alkali solution to form a pattern. Then, a post-baking heat treatment was performed at 140 ° C for 3 minutes before the etching step. This resist pattern was used as a mask, and it was immersed in an ITO etchant (3% aqueous oxalic acid solution) at 40 ° C / 1 min, whereby pattern processing of ITO was performed by wet etching. Then, it was immersed in a resist stripper (MS2001, manufactured by FUJIFILM Electronic Materials Co., Ltd.) at 70 ° C / 7 min to peel off the resist pattern. The first electrode 5 obtained in the above manner corresponds to the anode of the organic EL element.

Then, an insulating film 8 covering the shape of the periphery of the first electrode 5 is formed. The insulating film 8 is formed on the insulating film 8 by the same method as described above, using the photosensitive resin composition described in Example 1 of JP-A-2009-98616. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent step can be prevented.

Further, in the vacuum vapor deposition apparatus, a hole transport layer, an organic light-emitting layer, and an electron transport layer are sequentially deposited by interposing a desired pattern mask. Yu Ji A second electrode containing Al is formed on the entire upper surface of the plate. The obtained substrate was taken out from the vapor deposition machine, and sealed with a sealing glass plate by using an ultraviolet curable epoxy resin.

In the above-described manner, an organic EL display device having an active matrix ITO pattern in which the TFTs 1 for driving the TFTs 1 are connected to each of the organic EL elements is obtained. When a voltage is applied via a drive circuit, it is understood that the organic EL display device exhibits excellent display characteristics and high reliability.

(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 liquid crystal display device described in FIG. 1 of the Japanese Patent No. 3321003, the pixel electrode 4 is formed using the photosensitive resin composition of the first embodiment as a mask, and the liquid crystal display device of the seventeenth embodiment is obtained.

In other words, the pixel electrode 4 is formed by the same method as the method of forming the first electrode 5 of the organic EL display device of the above-described Embodiment 16.

When a driving voltage was applied to the obtained liquid crystal display device having an ITO pattern, it was found that the liquid crystal display device exhibited excellent display characteristics and high reliability.

1‧‧‧TFT (thin film transistor)

2‧‧‧Wiring

3‧‧‧Insulation film

4‧‧‧Flat film

5‧‧‧First electrode

6‧‧‧ glass substrate

7‧‧‧Contact hole

8‧‧‧Insulation film

Claims (15)

A photosensitive resin composition comprising: (A1) a polymer component, comprising a polymer comprising the structural unit (a1) represented by the following formula (1); (B) a photoacid generator; (C) a lipid a cyclic epoxy compound; and (D1) a solvent having two or more acetate structures in the molecule; (In the 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; and R ³ represents an alkyl group or an aromatic group; A group, R ¹ or R ² may be bonded to R ³ to form a cyclic ether; R ⁴ represents a hydrogen atom or a methyl group). The photosensitive resin composition according to claim 1, wherein the (C) alicyclic epoxy compound is a compound represented by the following formula (I): (In the above formula (I), n represents an integer of 1 to 4; and R ¹ represents an organic group having 1 to 15 carbon atoms). The photosensitive resin composition according to claim 2, wherein n in the compound represented by the above formula (I) is 1 or 2. The photosensitive resin composition according to claim 1 or 2, further comprising (A2) a polymer component, wherein the (A2) polymer component comprises a protective carboxyl group having an acid-decomposable group. Forming unit (a4). The photosensitive resin composition according to claim 4, wherein the structural unit (a4) is a structural unit represented by the following general formula (A2'): (In the formula (A2'), 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, and R ³ represents an alkyl group or An aryl group, R ¹ or R ² may be bonded to R ³ to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or an extended aryl group. The photosensitive resin composition according to claim 1 or 2, wherein the (C) alicyclic epoxy compound is contained in an amount relative to the total solid content The amount is 0.05% by mass to 5% by mass. The photosensitive resin composition according to the above-mentioned item (1), which contains the solvent having two or more acetate structures in the molecule (D1) and two molecules in the above (D1). The solvent of the above acetate structure is different from the other solvent (D2). The photosensitive resin composition according to the above-mentioned item (1), 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. The photosensitive resin composition according to the above-mentioned item (1), wherein the content of the solvent containing two or more acetate structures in the molecule (D1) is 1% by mass of the photosensitive resin composition. ~10% by mass. The photosensitive resin composition according to the above-mentioned item (1), which contains the solvent having two or more acetate structures in the molecule (D1) and two molecules in the above (D1). The solvent having a different acetate structure has a different solvent (D2), and the solvent having two or more acetate structures in the above (D1) molecule has a boiling point of 130 ° C or more and less than 300 ° C. A method for producing a pattern, comprising: (1) a step of coating a photosensitive resin composition according to any one of claims 1 to 10 on at least one side of a substrate; (2) a step of drying the organic solvent to form a photosensitive resin composition layer; (3) a step of exposing the photosensitive resin composition layer; (4) A step of developing the exposed photosensitive resin composition layer. The method for producing a pattern according to claim 11, comprising the steps of: etching using the formed pattern as an etching resist, and removing the pattern by plasma treatment or chemical treatment. . A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 10. A method of manufacturing an organic EL display device, comprising the method of producing a pattern according to claim 11 of the patent application. A method of manufacturing a liquid crystal display device comprising the method of producing a pattern according to claim 11 of the patent application.