WO2015064555A1

WO2015064555A1 - Photosensitive resin composition, pattern manufacturing method, cured film, organic el display device manufacturing method, and liquid crystal display device manufacturing method

Info

Publication number: WO2015064555A1
Application number: PCT/JP2014/078559
Authority: WO
Inventors: 藤本　進二; 史絵山下; 豪安藤; 大助柏木
Original assignee: 富士フイルム株式会社
Priority date: 2013-10-28
Filing date: 2014-10-28
Publication date: 2015-05-07
Also published as: JP6216801B2; JPWO2015064555A1

Abstract

Provided are a photosensitive resin composition which has good sensitivity, line width stability and separability, a pattern manufacturing method, a cured film, and an organic EL display device and liquid crystal display device manufacturing method. Relative to the total solid content, this photosensitive resin composition contains 0.01-5 mass% of (A1) a polymer having a constituent unit (a1) represented by general expression (1), (B) a photoacid generator having a 500 or greater molar extinction coefficient in 365nm-wavelength light, and (C) an alicyclic epoxy compound. In general expression (1), R¹ and R² independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R¹ and R² is an alkyl group or an aryl group; R³ represents an alkyl group or an aryl group, and may bind to R¹ or R² to form a cyclic ether; and R⁴ represents a hydrogen atom or a methyl group.

Description

Photosensitive resin composition, pattern manufacturing method, cured film, organic EL display device manufacturing method, and liquid crystal display device manufacturing method

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

The TFT (Thin Film Transistor) substrate used in flat panel display devices such as organic EL display devices and liquid crystal display devices has an insulating inorganic transparent film such as SiOx and SiNx, and an oxide transparent conductive film such as ITO and IZO. , Al, Mo, Ti, Cu, W, a metal film made of a laminated film thereof, and a semiconductor film such as Si or an oxide semiconductor are provided in a pattern. For pattern formation of these functional inorganic films, a photosensitive resin composition (etching resist) is applied to each functional inorganic film, solvent removal, pattern exposure and development are performed, and etching is performed using the formed resist pattern as a mask. A method of performing processing is widely known.

In recent years, in order to make organic EL display devices and liquid crystal display devices have high-definition display characteristics, high resolution of functional inorganic film processing is required. In order to finely process a functional inorganic film with high definition, high resolution of a photosensitive resin composition for an etching resist that functions as a mask during etching is required. For this reason, the photosensitive resin composition for etching resists from which a high-definition and fine pattern shape is obtained is examined (for example, patent document 1).

JP 2013-15694 A

In recent years, in order to produce a high-definition display panel substrate with high productivity, production using a large-area glass substrate has become common. In addition to sensitivity, the photosensitive resin composition for etching resist used for this is also required to have line width stability and peelability.

The present invention has been made to solve such a demand, and maintains a high sensitivity, a photosensitive resin composition having good line width stability and peelability, and a pattern manufacturing method using the same. An object of the present invention is to provide a method for producing a cured film, an organic EL display device, and a liquid crystal display device.

Under such circumstances, as a result of intensive studies by the present inventor, sensitivity and line width are obtained by adding a predetermined amount of an alicyclic epoxy compound to a polymer component containing a polymer having a structural unit having a predetermined structure. The present inventors have found that stability and peelability are good and have completed the present invention.
Specifically, the above problem has been solved by the following means.
<1> (A1) A polymer containing the structural unit (a1) represented by the following general formula (1), (B) a photoacid generator having a molar extinction coefficient of 500 or more at a wavelength of 365 nm, and (C ) A photosensitive resin composition containing 0.01 to 5% by mass of an alicyclic epoxy compound based on the total solid content;
General formula (1)

In general formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is an alkyl group or Represents an aryl group, and R ¹ or R ² and R ³ may be linked to form a cyclic ether, and R ⁴ represents a hydrogen atom or a methyl group.
<2> (C) The photosensitive resin composition according to <1>, wherein the alicyclic epoxy compound is a compound represented by the following general formula (I);
Formula (I)

In general formula (I), n represents an integer of 1 to 4. R represents an organic group having 1 to 15 carbon atoms.
<3> R in the general formula (I) is a hydrocarbon group or a combination of a hydrocarbon group and at least one of a silyl group, —O—, —CO—, —S— and —NR ¹ —. The photosensitive resin composition according to <2>, which is a group; wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms.
<4> (C) The photosensitive resin composition according to <1>, wherein the alicyclic epoxy compound is a compound represented by the following general formula (II);
Formula (II)

In the general formula (II), R ² represents an organic group having 1 to 15 carbon atoms.
<5> (C) The photosensitive resin composition according to <1>, wherein the alicyclic epoxy compound is a compound represented by the following general formula (III);
Formula (III)

In general formula (III), R ³ represents an organic group having 1 to 14 carbon atoms.
<6> (A1) The photosensitive resin composition according to any one of <1> to <5>, wherein the polymer further includes a structural unit (a4) represented by the following general formula (5):
General formula (5)

In general formula (5), R ⁴ is a hydrogen atom or a methyl group.
<7> The photosensitive resin composition according to any one of <1> to <6>, further including a polymer (A2) having a structural unit (a2) represented by the following general formula (2):
General formula (2)

In general formula (2), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least ^one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is an alkyl group R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or an arylene group. To express.
<8> The photosensitive resin composition according to any one of <1> to <7>, wherein the content of (C) the alicyclic epoxy compound is 0.05 to 3% by mass relative to the total solid content. .
<9> The photosensitive resin composition according to any one of <1> to <8>, further comprising (D) a basic compound.
<10> (D) The photosensitive resin composition according to <9>, wherein the basic compound is a compound represented by the following general formula (4);
General formula (4)

In general formula (4), R ¹ represents a group containing at least one nitrogen atom, A represents a divalent linking group, and R ² represents an organic group.
<11> The photosensitive resin composition according to any one of <1> to <10>, further comprising (E) an azole compound.
<12> The photosensitive resin composition according to <11>, wherein the (E) azole compound is one or more selected from the following general formulas (X1) to (X5):

In the formula, X represents CR ^x1 R ^X2 , NR ^x3 , O, or S;
Y and Z each independently represent CR ^x4 or N;
R ¹ , R ² , R ^X1 , R ^X2 , R ^X3 and R ^X4 each independently represent a hydrogen atom, a mercapto group, an amino group or an alkyl group,
R ⁴ represents an alkyl group, a mercapto group, an amino group, an alkoxy group, or an aralkyl group,
m represents an integer of 0 to 4, and when m is 2 or more, each R ⁴ may be the same or different;
At least one of X, Y and Z represents NR ^x3 or N.
<13> (1) A step of applying the photosensitive resin composition according to any one of <1> to <12> to at least one surface of the substrate,
(2) a step of drying the photosensitive resin composition to form a photosensitive resin composition layer;
(3) a step of exposing the photosensitive resin composition layer;
(4) A process for producing a pattern comprising a step of developing the exposed photosensitive resin composition layer.
<14> The method according to <13>, further including (5) a step of etching using the formed pattern as an etching resist, and (6) a step of removing the pattern by plasma treatment or chemical treatment. Pattern manufacturing method.
<15> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <12>.
<16> A method for producing an organic EL display device, comprising the method for producing a pattern according to <13> or <14>.
<17> A method for producing a liquid crystal display device, comprising the method for producing a pattern according to <13> or <14>.

According to the present invention, it is possible to provide a photosensitive resin composition having good line width stability and good peelability while maintaining high sensitivity. Moreover, it has become possible to provide a method for producing a pattern, a cured film, and a method for producing an organic EL display device and a liquid crystal display device, to which the photosensitive resin composition is applied.

1 shows a conceptual diagram of a configuration of an example of an organic EL display device. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device. 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device. 1 is a schematic cross-sectional view of an active matrix substrate in a liquid crystal display device. It is the figure which showed typically an example of the exposure form using a halftone phase difference mask. It is a composition conceptual diagram of an example of a touch panel display device.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. The organic EL element in the present invention refers to an organic electroluminescence element.

In addition, in the description of group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have 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).
Furthermore, (meth) acrylic acid means acrylic acid and / or methacrylic acid.

(Photosensitive resin composition)
The photosensitive resin composition of the present invention (hereinafter also referred to as “the composition of the present invention”) is (A1) a polymer having a structural unit (a1) represented by the following general formula (1), (B) 365 nm. A photoacid generator having a molar extinction coefficient of 500 or more in the light of the above wavelength and (C) an alicyclic epoxy compound is contained in an amount of 0.01 to 5% by mass based on the total solid content.
General formula (1)

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

By using the photosensitive resin composition of the present invention, line width stability and peelability are improved while maintaining high sensitivity. Although details of this mechanism are unknown, the structural unit (a1) is a weaker acid than the carboxylic acid, and an unnecessary crosslinking reaction with the acid hardly occurs. In addition, the alicyclic epoxy compound gently traps the acid generated from the photoacid generator and suppresses unnecessary crosslinking reaction. These are considered to improve the peelability. Moreover, it is thought that line width stability improves also by using an alicyclic epoxy compound.

The photosensitive resin composition of the present invention is usually used as a chemically amplified positive photosensitive resin composition. Hereinafter, the composition of the present invention will be described in detail.

<Polymer component (A)>
The photosensitive resin composition of this invention contains the polymer which has a structural unit (a1) represented by (A1) following general formula (1) as a polymer component (A). Further, (A2) a polymer having a structural unit (a2) represented by the following general formula (2) may be included.
(A1) The polymer may contain structural units other than the structural unit (a1) represented by General formula (1). Moreover, the (A2) polymer may also contain structural units other than the structural unit (a2) represented by General formula (2).
Hereinafter, these polymers will be described.

<< Polymer (A1) >>
The (A1) polymer in the present invention is a polymer including a polymer having the structural unit (a1) represented by the general formula (1). When the component (A1) has the structural unit (a1), a photosensitive resin composition excellent in resolving power and rectangularity can be obtained.

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.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. The alkyl group may have a substituent. The alkyl group may be linear, branched or cyclic, but is preferably a linear alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, and a cyclohexyl group.
As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 14 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is further preferable. The aryl group may have a substituent. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group.

Examples of the substituent that the alkyl group and 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, and a cyano group. And halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom) and the like. These substituents may further have a substituent.

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

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

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

Hereinafter, 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.

Among the structural units constituting the polymer (A1), the structural unit represented by the general formula (1) is preferably 5 to 50 mol%, preferably 5 to 40 mol% of all the structural units of the polymer (A1). More preferably, it is 10 to 40 mol%, further preferably 20 to 35 mol%.

The polymer (A1) preferably contains a structural unit (a4) represented by the following general formula (5) in addition to the structural unit (a1) from the viewpoint of high sensitivity.

(In general formula (5), R ⁴ is a hydrogen atom or a methyl group.)

R ⁴ is preferably a hydrogen atom.
The OH group may be any of p-, m-, and o-, but is preferably bonded to the p-position.

The structural unit represented by the general formula (5) is preferably 50 to 95 mol%, more preferably 50 to 80 mol%, still more preferably 60 to 80 mol%, based on all the structural units of the polymer (A1). 65 to 80 mol% is particularly preferred. By setting it in such a range, it becomes possible to keep the exposure process margin more appropriate.

(A1) The polymer may contain a structural unit other than the structural unit (a1) represented by the general formula (1) and the structural unit (a4) represented by the general formula (5). Specifically, the structural unit (for example, structural unit (a2)) and the structural unit (a3) which have the protected carboxyl group protected by the acid-decomposable group mentioned later are illustrated. However, in the present invention, in the polymer (A1), it is preferable that other structural units other than (a1) and (a4) are 10 mol% or less of the total structural units, more preferably 5 mol of the total structural units. % Or less.

(A1) The protection rate of the polymer is preferably 1 to 60%, more preferably 5 to 50%, and still more preferably 10 to 40%. By setting it as such a range, an image disk and a sensitivity, resolution, and rectangularity will become favorable. The protection rate refers to the molar ratio of the acid-protected structural unit, where the total of the acidic structural unit and the acid-protected structural unit in the polymer (A1) is 100 mol%.

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

The polydispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polymer (A1) is preferably 1.0 to 3.0, more preferably 1.0 to 2.0. 0 to 1.5 is more preferable. By setting it as such a range, the rectangularity of a pixel becomes favorable.

<< Polymer (A2) >>
In the present invention, (A2) a polymer may be included. (A2) The polymer has a protected carboxyl group protected with an acid-decomposable group. Examples of the structural unit having a protected carboxyl group protected by an acid-decomposable group include the structural unit having a protected carboxyl group protected by an acid-decomposable group described in paragraphs 0021 to 0055 of JP2012-155288A. Examples of the structural unit having a protected carboxyl group protected with an acid-decomposable group described in paragraphs [0020] to [0052] of JP 2012-133301 A are exemplified, the contents of which are incorporated herein. Among them, the polymer (A2) is preferably a polymer having a structural unit (a2) having a group in which an acid group having a structure represented by the following general formula (2) is protected with an acid-decomposable group. The acid group in the present invention means a proton dissociable group having a pKa of less than 7. The acid group is usually incorporated into the polymer as a structural unit containing an acid group using a monomer capable of forming an acid group. By including such a structural unit containing an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer. When the component (A2) has the structural unit (a2), a highly sensitive photosensitive resin composition can be obtained.

(A2) The polymer is preferably alkali-insoluble, and is preferably a resin that becomes alkali-soluble when the acid-decomposable group is decomposed. The structural unit having a protected carboxyl group in which the carboxyl group is protected with an acid-decomposable group can generate a carboxyl group by the decomposition of the protective group with an acid. Here, in the present invention, “alkali-soluble” means a coating film (thickness 3 μm) of a compound (resin) formed by applying a compound (resin) solution on a substrate and heating at 90 ° C. for 2 minutes. The dissolution rate in a 0.4% tetramethylammonium hydroxide aqueous solution at 23 ° C. is 0.01 μm / second or more. “Alkali insoluble” means that a compound (resin) solution is applied onto a substrate. The dissolution rate of the coating film (thickness 3 μm) of the compound (resin) formed by heating at 90 ° C. for 2 minutes with respect to a 0.4% tetramethylammonium hydroxide aqueous solution at 23 ° C. is 0.01 μm / It means less than a second.

(In the general formula (2), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least ^one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is Represents an alkyl group or an aryl group, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or an arylene group. Represents.)

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. Alkyl groups R ¹ and R ² represents the general formula (1) has the same meaning as the alkyl group R ¹ and R ² represents a preferred range is also the same. As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 14 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is further preferable. The aryl group may have a substituent. As an aryl group, a phenyl group, a naphthyl group, an anthracenyl group etc. are illustrated, for example, Among these, a phenyl group is preferable. 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, and the alkyl group and aryl group represented by R ³ are synonymous with the alkyl group and aryl group represented by R ³ in the general formula (1), and the preferred ranges are also the same. . Among them, R ³ is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
X ⁰ represents a single bond or an arylene group. As the arylene group, an arylene group having 6 to 20 carbon atoms is preferable, an arylene group having 6 to 14 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is more preferable. Examples of the arylene group include a phenylene group, a naphthylene group, and an anthracenylene group. The arylene group may have a substituent, and the substituent is synonymous with the substituent that the alkyl group represented by R ¹ and R ² in General Formula (1) may have. X ⁰ is preferably a single bond.

Preferable specific examples of the structural unit represented by the general formula (2) include the following structural units. R represents a hydrogen atom or a methyl group.

The structural unit (a2) represented by the general formula (2) is preferably 10 to 80 mol%, more preferably 20 to 80 mol%, more preferably 30 to 70 mol% of the structural unit of the polymer (A2). 30 to 45 mol% is more preferable.

(A2) The polymer may contain other structural units, and specific examples include structural units (a3) and (a4) described later.

In the polymer (A2) in the present invention, the content of other structural units, when included, is preferably 20 to 90 mol%, more preferably 20 to 80 mol%, still more preferably 30 to 70 mol%, and more preferably 55 to 70 mol% is particularly preferred. When it is within the above numerical range, various properties of the cured film obtained from the photosensitive resin composition are improved.
Moreover, in this invention, the other structural unit in (A2) polymer can also be set as the aspect of 10 mol%, Furthermore, 5 mol% or less.

(A2) The protection rate of the polymer is preferably 20 to 100%, more preferably 40 to 90%, and still more preferably 60 to 90%. By setting it as such a range, a sensitivity improves and the difference (discrimination) of the solubility of an exposed part and an unexposed part becomes favorable. The protection rate refers to the molar ratio of the acid-protected structural unit, where the total of the acidic structural unit and the acid-protected structural unit in the polymer (A2) is 100 mol%.

The weight average molecular weight (Mw) of the (A2) polymer is preferably in the range of 2000 to 50000, more preferably 5000 to 20000, and still more preferably 7500 to 15000. By setting it to 2000 or more, an effect that the formed pixel can maintain rectangularity after heating by post-baking is obtained, and by setting it to 50000 or less, an effect that sensitivity and PED characteristics are improved is obtained. Here, the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.

The polydispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polymer (A2) is preferably 1.0 to 4.0, more preferably 1.2 to 3.0. 5 to 2.0 is more preferable. By setting it as such a range, the characteristic excellent in the sensitivity and the rectangularity can be acquired.

-Mixing ratio of component (A1) and component (A2)-
The photosensitive resin composition of the present invention preferably contains both (A1) and (A2) as the polymer component. These mass ratios are preferably 2: 8 to 8: 2, more preferably 3: 7 to 7: 3, and still more preferably 4: 6 to 6: 4. By setting it as such a range, it exists in the tendency for the effect of this invention to be exhibited more effectively.

<< polymer component >>
In the present invention, the component (A) may have another polymer in addition to the above (A1) polymer and (A2) polymer. As another polymer, it is a polymer which does not contain a structural unit (a1) and a structural unit (a2), for example, the polymer which has a structural unit (a3) is illustrated. Such other polymer components are preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass or less in the total polymer components.

There is no restriction | limiting in particular as a structural unit (monomer) used as another structural unit (a3), For example, styrenes, (meth) acrylic-acid alkylester, (meth) acrylic-acid cyclic alkylester, (meth) acrylic-acid aryl Esters, unsaturated dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, other unsaturated compounds Mention may be made of saturated compounds. Moreover, you may have the structural unit which has an acid group so that it may mention later. By including a structural unit having an acid group, the sensitivity can be improved. As the structural unit having an acid group, acrylic acid, methacrylic acid, and other monomers to be the structural unit (a3) can be used alone or in combination of two or more.

In this invention, it is preferable that the structural unit which has an acid group is included as another structural unit (a3). By containing an acid group, it becomes easy to dissolve in an alkaline developer, and the effects of the present invention are more effectively exhibited.
The acid group in the present invention means a proton dissociable group having a pKa of less than 7. The acid group is usually incorporated into the polymer as a structural unit containing an acid group using a monomer capable of forming an acid group. By including such a structural unit containing an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer.
Acid groups used in the present invention include those derived from carboxylic acid groups, those derived from sulfonamide groups, those derived from phosphonic acid groups, those derived from sulfonic acid groups, those derived from phenolic hydroxyl groups, sulfones Amide groups, sulfonylimide groups and the like are exemplified, and those derived from carboxylic acid groups and / or those derived from phenolic hydroxyl groups are preferred.
The structural unit containing an acid group used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, a structural unit derived from (meth) acrylic acid and / or an ester thereof. .

In the present invention, it is particularly preferable from the viewpoint of sensitivity to include a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group.

The structural unit containing an acid group is preferably 1 to 80% by mole, more preferably 1 to 50% by mole, and still more preferably 5 to 40% by mole of the structural unit of all polymer components.

Such a polymer is preferably a resin having a carboxyl group in the side chain. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain Examples thereof include acidic cellulose derivatives having a carboxyl group, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, and high molecular polymers having a (meth) acryloyl group in the side chain.

For example, benzyl (meth) acrylate / (meth) acrylic acid co-A-2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, described in JP-A-7-140654 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid co-A-2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid co-A-2-hydroxyethyl Methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer A-2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer It is below.
In addition, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118 Known polymer compounds described in JP-A-2003-233179, JP-A-2009-52020, and the like can be used, and the contents thereof are incorporated herein.

As these polymers, commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA ４０ 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above, manufactured by Sartomer), ARUFON UC-3000, ARU FON Ｃ UC-3510, ARU FON UC -3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), Joncryl 690, Joncryl 678, Joncryl 67, Joncryl 586 (above, also made by BASF), etc. it can.

These polymers may contain only 1 type and may contain 2 or more types.
The composition of the present invention preferably contains the polymer component in a proportion of 60% by weight or more, more preferably 80% by weight or more, based on the total solid content.

<(B) Photoacid generator>
The photosensitive resin composition of the present invention contains (B) a photoacid generator having a molar extinction coefficient of 500 or more in light having a wavelength of 365 nm. As the photoacid generator (also referred to as “component (B)”) used in the present invention, a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid is preferable. The chemical structure is not limited.
Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination. The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and an acid of 2 or less. Most preferred are photoacid generators that generate.
A known method can be used for the molar extinction coefficient of the photoacid generator. Specifically, for example, an ethyl acetate solvent is used in an ultraviolet-visible spectrophotometer (Vary Inc., Carry-5 spectrphotometer). It is preferable to measure at a concentration of 0.01 g / L.

Examples of the photoacid generator include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation. These photoacid generators can be used singly or in combination of two or more. Specific examples of trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives include the compounds described in paragraph numbers 0083 to 0088 of JP2011-212494A. It can be illustrated.

Preferred examples of the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure include compounds having an oxime sulfonate structure represented by the following general formula (B1).

General formula (B1)

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

Any group may be substituted, and the alkyl group in R ²¹ may be linear, branched or cyclic. Acceptable substituents are described below.
The alkyl group for R ²¹ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group represented by R ²¹ is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group or the like). It may be substituted with a cyclic group, preferably a bicycloalkyl group or the like.
As the aryl group for R ^21, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ²¹ may be substituted with a lower alkyl group, an alkoxy group, or a halogen atom.

The above compound containing an oxime sulfonate structure represented by the above general formula (B1) is also preferably an oxime sulfonate compound represented by the following general 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 m4 represents 2 or When X is 3, the plurality of X may be the same or 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 general formula (B2), m4 is 1, X is a methyl group, the substitution position of X is the ortho position, R ⁴² is a linear alkyl group having 1 to 10 carbon atoms, 7,7- A compound that is a dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferred.

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

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

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

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

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

The compound containing an oxime sulfonate structure represented by the above general formula (B1) is also preferably a compound represented by the following general formula (3).

(In the general formula (3), R ¹ represents an alkyl group or an aryl group, R ² represents an alkyl group, an aryl group, or a heteroaryl group. R ³ to R ⁶ represent a hydrogen atom or an alkyl group, respectively. A group, an aryl group, or a halogen atom, provided that R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ may combine to form an alicyclic ring or an aromatic ring, and X is — Represents O- or -S-)

R ¹ represents an alkyl group or an aryl group. The alkyl group is preferably a branched alkyl group or a cyclic alkyl group. The alkyl group preferably has 3 to 10 carbon atoms. In particular, when the alkyl group has a branched structure, an alkyl group having 3 to 6 carbon atoms is preferable. When the alkyl group has a cyclic structure, an alkyl group having 5 to 7 carbon atoms is preferable. Examples of the alkyl group include propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 1,1-dimethylpropyl group, hexyl group. , 2-ethylhexyl group, cyclohexyl group, cyclopentyl group, octyl group and the like, preferably isopropyl group, tert-butyl group, neopentyl group, and cyclohexyl group. The aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, and still more preferably 6 to 7 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.
The alkyl group and aryl group represented by R ¹ may have a substituent. Examples of the substituent include a halogen atom (a fluorine atom, a chloro atom, a bromine atom, an iodine atom), a linear, branched or cyclic alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.), an alkenyl group, an alkynyl group, Aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, carboxyl group, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic oxy group, acyloxy group, amino group, A nitro group, a hydrazino group, a heterocyclic group, etc. are mentioned. Further, these groups may be further substituted. Preferably, they are a halogen atom and a methyl group.

In the photosensitive resin composition of the present invention, R ¹ is preferably an alkyl group from the viewpoint of transparency, and R ¹ has a branched structure having 3 to 6 carbon atoms from the viewpoint of achieving both storage stability and sensitivity. An alkyl group, an alkyl group having a cyclic structure having 5 to 7 carbon atoms, or a phenyl group is preferable, and an alkyl group having a branched structure having 3 to 6 carbon atoms or an alkyl group having a cyclic structure having 5 to 7 carbon atoms is more preferable. . By adopting such a bulky group (particularly a bulky alkyl group) as R ¹ , it becomes possible to further improve the transparency.
Among the bulky substituents, an isopropyl group, a tert-butyl group, a neopentyl group, and a cyclohexyl group are preferable, and a tert-butyl group and a cyclohexyl group are more preferable.

R ² represents an alkyl group, an aryl group, or a heteroaryl group. The alkyl group represented by R ² is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, and a cyclohexyl group. It is a group.
As the aryl group, an aryl group having 6 to 10 carbon atoms is preferable. Examples of the aryl group include a phenyl group, a naphthyl group, a p-toluyl group (p-methylphenyl group), and a phenyl group and a p-toluyl group are preferable. Examples of the heteroaryl group include a pyrrole group, an indole group, a carbazole group, a furan group, and a thiophene group.
The alkyl group, aryl group, and heteroaryl group represented by R ² may have a substituent. As a substituent, it is synonymous with the substituent which the alkyl group and aryl group which R < ¹ > may have.
R ² is preferably an alkyl group or an aryl group, more preferably an aryl group, and more preferably a phenyl group. As the substituent for the phenyl group, a methyl group is preferred.

R ³ to R ⁶ each represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom). The alkyl group represented by R ³ to R ⁶ has the same meaning as the alkyl group represented by R ² , and the preferred range is also the same. The aryl group represented by R ³ to R ⁶ has the same meaning as the aryl group represented by R ¹ , and the preferred range is also the same.
Among R ³ to R ⁶ , R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ may combine to form a ring, and the ring may form an alicyclic ring or an aromatic ring. It is preferable that a benzene ring is more preferable.
R ³ to R ⁶ are each a hydrogen atom, an alkyl group, a halogen atom (fluorine atom, chloro atom, bromine atom), or R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ^6. A benzene ring is preferably formed, and a hydrogen atom, a methyl group, a fluorine atom, a chloro atom, a bromine atom, or R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ are combined to form a benzene ring Is more preferable.
Preferred embodiments of R ³ to R ⁶ are as follows.
(Aspect 1) Preferably, at least one is a hydrogen atom and at least two are hydrogen atoms.
(Aspect 2) The number of alkyl groups, aryl groups, or halogen atoms is 3 or less in total. Preferably it is one or less.
(Aspect 3) R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ are combined to form a benzene ring.
(Aspect 4) An aspect satisfying the

above aspects

1 and 2 and / or an aspect satisfying the above aspects 1 and 3.

X represents -O- or -S-.

Specific examples of the general formula (3) include the following compounds, but the present invention is not particularly limited thereto. In the exemplified compounds, Ts represents a tosyl group (p-toluenesulfonyl group), Me represents a methyl group, Bu represents an n-butyl group, and Ph represents a phenyl group.

In the photosensitive resin composition of the present invention, (B) the photoacid generator is based on 100 parts by mass of all resin components (preferably the total solid content, more preferably the total of the polymer) in the photosensitive resin composition. 0.1 to 10 parts by mass is preferably used, and 0.5 to 5 parts by mass is more preferably used. (B) Only one type of acid generator may be used, or two or more types may be used in combination. (B) By making content of a photo-acid generator into 0.1 mass part or more, a sensitivity can be improved more effectively.

<(C) Alicyclic epoxy compound>
The photosensitive resin composition of the present invention contains 0.01 to 5% by mass of the alicyclic epoxy compound with respect to the total solid content.
The alicyclic epoxy group possessed by 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. Is preferably a 3- to 10-membered ring, more preferably a 5- to 6-membered ring. The cycloaliphatic hydrocarbon group is preferably a saturated cycloaliphatic hydrocarbon group. Among them, a compound having an alicyclic epoxy group represented by the following is preferable.

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

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

R represents an organic group having 1 to 15 carbon atoms, may be branched or have an unsaturated bond, and may have an aliphatic ring or an aromatic ring structure. In addition, these groups may have oxygen, sulfur, nitrogen, phosphorus, boron, and halogen atoms, but may not have such an embodiment. Moreover, you may have a substituent and substituents may mutually form a bond. Examples of the substituent are the general formula (1) R ¹ and R ² are synonymous with the substituent which may be possessed by the alkyl groups represented in. R ¹ is an n-valent linking group.

The organic group of R preferably has 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms. The organic group is a hydrocarbon group or a hydrocarbon group and a silyl group, —O—, —CO—, —S—, and —NR ¹ — (R ¹ is a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. And a group consisting of a hydrocarbon group or a combination of a hydrocarbon group and —O— and / or —CO— is more preferable. The hydrocarbon group is preferably a linear or branched group, and more preferably a linear group. The hydrocarbon group preferably has 1 to 4 carbon atoms. Two or more hydrocarbon groups may be contained in one organic group.

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 degree of freedom of the alicyclic epoxy compound is increased. May be lost. For this reason, it is preferable that the number of epoxy groups is small. n represents an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 1 or 2.

As a preferable aspect of an alicyclic epoxy compound, the compound represented by the following general formula (II) is illustrated.
Formula (II)

(In the general 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 or have an unsaturated bond, and may have an aliphatic ring or an aromatic ring structure. These groups may have oxygen, sulfur, nitrogen, phosphorus, boron, or halogen atoms. Moreover, you may have a substituent and substituents may mutually couple | bond together. Examples of the substituent are the general formula (1) R ¹ and R ² are synonymous with the substituent which may be possessed by the alkyl groups represented in. R ² is a divalent linking group.

The organic group of R ² preferably has 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms. The organic group is a hydrocarbon group or a hydrocarbon group and —O—, —CO—, —S— and —NR ¹ — (R ¹ represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms). And a group consisting of a hydrocarbon group or a combination of a hydrocarbon group and —O— and / or —CO— is more preferable. The hydrocarbon group is preferably a linear or branched group, and more preferably a linear group. The hydrocarbon group preferably has 1 to 4 carbon atoms. Two or more hydrocarbon groups may be contained in one organic group. The hydrocarbon group is preferably an alkylene group.

As a preferable aspect of an alicyclic epoxy compound, the compound represented by the following general formula (III) is also illustrated.
Formula (III)

(In the general formula (III), R ³ represents an organic group having 1 to 14 carbon atoms.)

R ³ represents an organic group having 1 to 14 carbon atoms, may be branched or have an unsaturated bond, and may have an aliphatic ring or an aromatic ring structure. These groups may have oxygen, sulfur, nitrogen, phosphorus, boron, or halogen atoms. Moreover, you may have a substituent and substituents may mutually form a bond. R ³ is a divalent linking group.

The number of carbon atoms in the organic group of R ³ is preferably 1-8, and more preferably 1-6. The organic group is a hydrocarbon group or a hydrocarbon group and —O—, —CO—, —S— and —NR ¹ — (R ¹ represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms). And a group consisting of a hydrocarbon group or a combination of a hydrocarbon group and —O— and / or —CO— is more preferable. The hydrocarbon group is preferably a linear or branched group, and more preferably a linear group. The hydrocarbon group preferably has 1 to 4 carbon atoms. Two or more hydrocarbon groups may be contained in one organic group. The hydrocarbon group is preferably an alkylene group.

Specific examples of the general formulas (I) to (III) include the following compounds, but the present invention is not particularly limited thereto. Me represents a methyl group.

The production method of the alicyclic epoxy compound used in the present invention is not limited. For example, Maruzen KK Publishing, 4th Edition Experimental Chemistry Course 20 Organic Synthesis II, 213-, 1992, Ed. by Alfred Hasfner, The chemistry of heterocyclic compounds-Small Ring Heterocycles part3 oxiranes, John & Wiley and Sons, An Interscience Publication, New York, 1985, Yoshimura, adhesive, Vol. 29 No. 12, 32,1985, Yoshimura, adhesive, Vol. 30, No. 5 42, 1986, Yoshimura, Adhesion, Vol. 30, No. 7, 42, 1986, JP-A-1-100388, Japanese Patent No. 2906245, Japanese Patent No. 2926262, and the like.

The molecular weight of the alicyclic epoxy compound used in the present invention is less than 1000, and preferably less than 500. By setting it as such a range, it exists in the tendency for the effect of this invention to be exhibited more effectively. The lower limit is not particularly defined, but is usually 100 or more.

The addition amount of the alicyclic epoxy compound in the photosensitive resin composition of the present invention is 0.01 to 5% by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition, and 0.05 to 5%. It is preferably part by weight, more preferably 0.05 to 4 parts by weight, still more preferably 0.05 to 3 parts by weight, and particularly preferably 0.07 to 1.8 parts by weight. preferable. Line width stability can be improved by setting the content of the alicyclic epoxy compound to 0.01% by mass or more, and peelability can be improved by setting the content to 5% by mass or less. An alicyclic epoxy compound may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of alicyclic epoxy compounds, the total amount becomes the said range.

<(D) Basic compound>
The composition of the present invention may contain (D) a basic compound. (D) It becomes possible to dope an acid rapidly by containing a basic compound. The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include the compounds described in JP-A 2011-212494, paragraphs 0204 to 0207, the contents of which are incorporated herein.
In addition, in this specification, (D) basic compound is compounds other than (E) azole compound mentioned later.
The basic compound is preferably a compound represented by the following general formula (4).
General formula (4)

(In General Formula (4), R ¹ represents a group containing at least one nitrogen atom, A represents a divalent linking group, and R ² represents an organic group.)

R ¹ represents a group containing at least one nitrogen atom, preferably a group containing 1 to 3 nitrogen atoms, and more preferably a group represented by —NR ³ R ⁴ .
R ¹ is preferably a group composed of a hydrocarbon group having 1 to 10 carbon atoms and 1 to 3 heteroatoms containing an oxygen atom, a sulfur atom, or at least one nitrogen atom. In this case, examples of the hetero atom include an oxygen atom and a sulfur atom, and an oxygen atom is preferable. R ¹ is preferably a cyclic group, more preferably a 5-membered or 6-membered cyclic group.
R ³ and R ⁴ each represents an organic group. As the organic group, an alkyl group, an alkenyl group, or a group composed of at least one of —O—, —S— and —N— is preferable. R ³ and R ⁴ are each preferably a group having 1 to 3 carbon atoms. R ³ and R ⁴ may be bonded to each other to form a ring, and preferably forms a ring.

Preferred embodiments of R ¹ include the following embodiments.
(1) An embodiment in which R ¹ is a group represented by —NR ³ R ⁴ and R ³ and R ⁴ are bonded to each other to form a ring, or R ³ and R ⁴ are each The aspect which is an aliphatic hydrocarbon group.
(2) Embodiment in which R ¹ is a group represented by —NR ³ R ⁴ and R ³ and R ⁴ are bonded to each other to form a 5-membered or 6-membered ring, or R ³ and R ⁴ Are each a linear or branched aliphatic hydrocarbon group having 1 to 4 carbon atoms.
(3) R ¹ is a group represented by —NR ³ R ⁴ , and R ³ and R ⁴ are bonded to each other to form two or more heteroatoms (at least one is a nitrogen atom and the rest are oxygen atoms or A mode in which a 5-membered ring or a 6-membered ring is formed, or a straight-chain aliphatic hydrocarbon group having 1 to 4 carbon atoms, each of R ³ and R ⁴ The aspect which is.

Specific examples of R ¹ include, for example, morpholino group, hydrazino group, pyridyl group, imidazolyl group, quinolyl group, piperidyl group, pyrrolidinyl group, pyrazonyl group, oxazolyl group, thiazolyl group, benzoxazolyl group, benzimidazolyl group, A benzthiazolyl group, a pyrazinyl group, a diethylamino group, etc. are mentioned. Of these, a morpholino group is preferable.

R ² represents an organic group. The organic group is preferably a hydrocarbon group or a group comprising a hydrocarbon group and at least one of —O— and —C (═O) —. R ² preferably has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms.
R ² is more preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, or a group consisting of these and at least one combination of —O— and —C (═O) —. These groups may have a substituent, and examples of the substituent include a halogen atom.
When R ² is an alkyl group, a linear or branched alkyl group having 1 to 8 carbon atoms or a cyclic alkyl group is preferable. When R ² is a cyclic alkyl group, a 5-membered or 6-membered cyclic alkyl group is preferred.
When R ² is an aryl group, a phenyl group and a naphthyl group are exemplified, and a phenyl group is more preferable.

A preferred embodiment of R ² is a straight chain alkylene group having 1 to 4 carbon atoms (preferably 2 or 3).

A represents a divalent linking group, preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 1 to 10 carbon atoms, and further preferably a hydrocarbon group having 2 to 6 carbon atoms. Examples of the hydrocarbon group include an alkylene group and an arylene group, and an alkylene group is preferable.
Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a cyclohexylene group, and a cyclopentylene group. Examples of the arylene group include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, and a naphthylene group. In the present invention, a methylene group, an ethylene group, and a propylene group are particularly preferable, and an ethylene group or a propylene group is more preferable.

A preferred embodiment of A is an embodiment which is a linear or branched alkyl group having 1 to 4 carbon atoms, a 5-membered or 6-membered cyclic alkyl group, or a phenyl group.

The compound represented by the general formula (4) is the preferred embodiment the R ^1, R 2 ² preferred embodiment, embodiment comprising a combination of preferred embodiments of A are exemplified as particularly preferred embodiment.

The compound represented by the general formula (4) is preferably represented by the general formula (4-2).
Formula (4-2)

(In the general formula (4-2), R ² represents an organic group, and A represents a divalent linking group.)

R ² has the same meaning as R ² in the formula (4), the preferred range is also the same.
A is synonymous with A in the above formula (4), and a preferred range is also synonymous.
In particular, in the general formula (4-2), the following embodiments are preferable.
(1) An embodiment in which A is a linear alkylene group having 1 to 4 carbon atoms, and R ² is a linear, branched, or cyclic alkyl group.
(2) A mode in which A is an alkylene group having 2 or 3 carbon atoms, and R ² is a linear, branched or cyclic alkyl group having 2 to 6 carbon atoms.

Specific examples of the general formula (4) include the following compounds, but the present invention is not particularly limited thereto. In the exemplified compounds, Et represents an ethyl group.

In addition to the above, examples of basic compounds that can be used in the present invention include compounds represented by general formula (b) in paragraph No. 0110 of JP2013-015694A, and compounds represented by general formula (c). These contents can be preferably adopted, and the contents thereof are incorporated in the present specification.

When the photosensitive resin composition of the present invention contains (D) a basic compound, the content of (D) the basic compound is 0.001 to 5 masses of component (D) with respect to 100 mass parts of the total solid content. Preferably, it is contained at a rate of 0.003 to 2 parts by mass, more preferably at a rate of 0.005 to 1 part by mass, and 0.01 to 0.09 parts by mass. It is particularly preferable to include within the range of parts. Sensitivity can be improved by making content of a basic compound into 5 mass parts or less. (D) Only 1 type may be sufficient as a component and 2 or more types may be sufficient as it. In the case of two or more types, the total is preferably in the above range.

In the composition of the present invention, the mass ratio of (C) the alicyclic epoxy compound and (D) the basic compound is preferably 100: 1 to 100: 100, and preferably 100: 10 to 100: 50. More preferred. (C) The alicyclic epoxy compound acts as a weaker quencher and gently dopes the acid generated from the acid generator. On the other hand, the basic compound (D) quickly dopes the acid generated from the acid generator. Therefore, by setting it as the said mass ratio, both components work | function more well and the effect of this invention is exhibited more effectively.

<(E) azole compound>
The composition of the present invention may contain (E) an azole compound. (E) By containing an azole compound, development adhesiveness improves and line width stability improves.
The azole compound is preferably at least one selected from the following general formulas (X1) to (X5).

In the formula, X represents CR ^x1 R ^X2 , NR ^x3 , O, or S;
Y and Z each independently represent CR ^x4 or N;
R ¹ , R ² , R ^X1 , R ^X2 , R ^X3 and R ^X4 each independently represent a hydrogen atom, a mercapto group, an amino group or an alkyl group,
R ⁴ represents an alkyl group, a mercapto group, an amino group, an alkoxy group, or an aralkyl group,
m represents an integer of 0 to 4, and when m is 2 or more, each R ⁴ may be the same or different;
At least one of X, Y and Z represents NR ^x3 or N.

The number of carbon atoms of the alkyl group represented by R ¹ , R ² , R ^X1 , R ^X2 , R ^X3 and R ^X4 is preferably 1 to 20, and more preferably 1 to 10. The alkyl group may be linear, branched or cyclic.

The alkyl group represented by R ⁴ preferably has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkyl group may be linear, branched or cyclic.
The number of carbon atoms of the alkoxy group represented by R ⁴ is preferably 1-20, and more preferably 1-10. The alkyl group may be linear or branched.
The number of carbon atoms in the aralkyl group represented by R ⁴ is preferably 7 to 20, and more preferably 7 to 10.

m represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.
Specific examples of the azole compound include 2-mercaptobenzimidazole (E-1 below),
2,5-dimercapto-1,3,4-thiadiazole (E-2 below), 2-mercaptobenzothiazole (E-3 below), 2-mercaptoimidazoline (E-4 below), 2-mercaptothiazoline (E below) -5), 2-aminothiazole (E-6 below), 3-amino-5-mercaptotriazole (E-7 below) and the like.

When the photosensitive resin composition of the present invention contains an azole compound, the content of the azole compound is preferably 0.1 to 10 parts by mass, and 0.5 to 5 parts by mass with respect to 100 parts by mass of the polymer component. More preferred. Line width stability can be improved more by making content of an azole compound into 0.1 mass part or more (preferably 0.5 mass part or more). Only one type of azole compound may be used, or two or more types may be used. In the case of two or more types, the total is preferably in the above range.

<Solvent>
The photosensitive resin composition of the present invention may contain a solvent. There is no restriction | limiting in particular as a solvent used for the composition of this invention, Although a well-known solvent can be used, It is preferable to use the solvent which contains two or more acetate structures in a molecule | numerator. By blending such a solvent, it becomes an appropriate plasticizer for the coating film, and by promoting the proper capture of the acid by the quencher and the alicyclic epoxy compound, sensitivity, line width stability It becomes possible to improve resolution and rectangularity. The photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and further optional components described below are dissolved in a solvent.

The solvent containing two or more acetate structures in the molecule is not particularly limited as long as it contains two or more acetate structures in the molecule, but the number of acetate structures in the molecule is preferably 2 to 4, and two more preferable.
The solvent having two or more acetate structures in the molecule is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 300 ° C., preferably a solvent having a boiling point of 180 ° C. or higher and lower than 270 ° C., and more preferably a solvent having a boiling point of 200 ° C. or higher and lower than 270 ° C. . The boiling point is a boiling point at 1 atm unless otherwise specified. Further, in the case of a solvent mixture containing two or more kinds of solvents, the boiling point is a weighted average of the boiling points of the respective solvents with respect to the total solvent at the respective weight ratios.

Examples of the solvent containing two or more acetate structures in the molecule include 1,2-ethylenediol diacetate, 1,2-propanediol diacetate, 1,3-propanediol diacetate, 1,2- Examples include butanediol diacetate, 1,3-butanediol diacetate, 1,4-butanediol diacetate, 1,6-hexanediol diacetate, and triacetin. (C1) The solvent containing two or more acetate structures in the molecule can be used alone or in admixture of two or more.

When the photosensitive resin composition of the present invention contains a solvent containing two or more acetate structures in the molecule, the content of the solvent is preferably 1 to 10% by mass of the total components of the photosensitive resin composition. More preferably, the content is 1 to 5% by mass.

In addition, it is preferable to add another solvent to the solvent containing two or more acetate structures in the molecule, if necessary, to obtain a mixed solvent. In the case of the above mixed solvent, it is preferable to select another solvent so that the weighted average of the boiling points of the respective solvents with respect to the total solvent is 130 ° C. or higher and lower than 300 ° C. Other solvents can be used singly or in combination of two or more.

The other solvent is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., or a solvent having a boiling point of 160 ° C. or higher. Specifically, propylene glycol monomethyl ether acetate (boiling point 146 ° C.) Examples thereof include solvents having one acetate structure in the molecule such as (boiling point 158 ° C.); propylene glycol methyl-n-butyl ether (boiling point 155 ° C.) and propylene glycol methyl-n-propyl ether (boiling point 131 ° C.).
Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate. (Bp 213 ° C.), 3-methoxybutyl ether acetate (bp 171 ° C.), diethylene glycol diethyl ether (bp 189 ° C.), diethylene glycol dimethyl ether (bp 162 ° C.), diethylene glycol monoethyl ether acetate (bp 220 ° C.), dipropylene glycol dimethyl ether ( A boiling point of 175 ° C.).

In addition to the other solvents, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers. , Propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones And amides and lactones. In addition, specific examples of other solvents used in the photosensitive resin composition of the present invention include the solvents described in paragraph numbers 0174 to 0178 of JP 2011-221494A, the contents of which are described in the present specification. Incorporated into.

If necessary, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonal, benzyl alcohol, Solvents such as anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, and propylene carbonate can also be added. These solvents can be used alone or in combination of two or more. The solvent that can be used in the present invention is a single type or a combination of two types, more preferably a combination of two types, propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates. And diethylene glycol dialkyl ethers or esters and butylene glycol alkyl ether acetates are more preferably used in combination.

When the photosensitive resin composition of the present invention contains another solvent, the content of the other solvent is preferably 70 to 95% by mass of the total components of the photosensitive resin composition, and is 85% by mass or more. More preferably it is.

<Other ingredients>
In addition to the above components, an alkoxysilane compound, a crosslinking agent, a sensitizer, a surfactant, and an antioxidant can be preferably added to the photosensitive resin composition of the present invention as necessary. Furthermore, the photosensitive resin composition of the present invention includes an acid proliferation agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor. Known additives such as can be added. Examples of the other components include compounds described in [0180] [0228] of JP2011-221494A.

<< alkoxysilane compound >>
The photosensitive resin composition of the present invention may contain an alkoxysilane compound. When an alkoxysilane compound is used, the adhesion between the film formed from the photosensitive resin composition of the present invention and the substrate can be improved, or the properties of the film formed from the photosensitive resin composition of the present invention can be adjusted. Can do. As the alkoxysilane compound, a dialkoxysilane compound or a trialkoxysilane compound is preferable, and a trialkoxysilane compound is more preferable. The alkoxy group contained in the alkoxysilane compound preferably has 1 to 5 carbon atoms.
The alkoxysilane compound that can be used in the photosensitive resin composition of the present invention is a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, molybdenum, titanium, or aluminum. Preferably, the compound improves the adhesion between the insulating film and the insulating film. Specifically, a known silane coupling agent or the like is also effective.
Examples of silane coupling agents include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, and γ-methacryloxy. Propyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Is mentioned. Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is more preferable. Further preferred. These can be used alone or in combination of two or more.

The following compounds can also be preferably employed.

In the above, Ph is a phenyl group.

The alkoxysilane compound in the photosensitive resin composition of this invention is not specifically limited to these, A well-known thing can be used.
When the photosensitive resin composition of the present invention contains an alkoxysilane compound, the content of the alkoxysilane compound is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive composition, 0.5 to 20 parts by mass is more preferable. An alkoxysilane compound may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of alkoxysilane compounds, the total amount becomes the said range.

<< Crosslinking agent >>
It is preferable that the photosensitive resin composition of this invention contains crosslinking agents other than the said (C) alicyclic epoxy compound as needed. By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made a stronger film.
The crosslinking agent is not limited as long as a crosslinking reaction is caused by heat. For example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, a compound having at least one ethylenically unsaturated double bond, a blocked isocyanate compound, etc. Can be added. Specific examples of the crosslinking agent include compounds described in [0187] to [0199] of JP2011-212494A.
When the photosensitive resin composition of the present invention contains a crosslinking agent, the addition amount of the crosslinking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition. The amount is more preferably 0.1 to 30 parts by mass, and further preferably 0.5 to 20 parts by mass. By adding in this range, a cured film having excellent mechanical strength and solvent resistance can be obtained. A plurality of crosslinking agents may be used in combination. In that case, the content is calculated by adding all the crosslinking agents. A crosslinking agent may be used individually by 1 type, or may use 2 or more types together. When two or more types of crosslinking agents are used, the total amount falls within the above range.

-Compounds with two or more epoxy groups or oxetanyl groups in the molecule-
Specific examples of compounds having two or more epoxy groups in the molecule include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins, and the like. Can do.

These are available as commercial products. Examples thereof include commercially available products described in paragraph No. 0189 of JP2011-212494, such as JER157S70 and JER157S65 (manufactured by Mitsubishi Chemical Holdings Corporation).
In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), 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- 14L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (all manufactured by Nagase ChemteX Corporation) ), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (manufactured by Nippon Steel Chemical Co., Ltd.) EHPE3150, Cellbiners B0134, B0177 (Daicel) .
These can be used alone or in combination of two or more.

Among these, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, aliphatic epoxies, and aliphatic epoxy resins are more preferable, and bisphenol A type epoxy resins are particularly preferable.

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

In addition, the compound containing an oxetanyl group is preferably used alone or mixed with a compound containing an epoxy group.

As other crosslinking agents, alkoxymethyl group-containing crosslinking agents described in paragraphs 0107 to 0108 of JP2012-8223A and compounds having at least one ethylenically unsaturated double bond are also preferably used. The contents of which are incorporated herein by reference. As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated glycoluril is preferable.

-Block isocyanate compounds-
In the photosensitive resin composition of the present invention, a blocked isocyanate compound can also be preferably employed as a crosslinking agent. The blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, but is preferably a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability.
In addition, the blocked isocyanate group in this invention is a group which can produce | generate an isocyanate group with a heat | fever, For example, the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably. The blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 ° C. to 250 ° C.
Further, the skeleton of the blocked isocyanate compound is not particularly limited and may be any as long as it has two isocyanate groups in one molecule, and is aliphatic, alicyclic or aromatic. Polyisocyanates may be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene 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 diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2 2'-diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1 , 4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-methylene ditolylene-4,4'-diisocyanate, 4,4'-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate , Isocyanation of hydrogenated 1,3-xylylene diisocyanate, hydrogenated 1,4-xylylene diisocyanate, etc. A compound and a prepolymer type skeleton compound derived from these compounds can be preferably used. Among these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.

Examples of the matrix structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to. Among these, a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.

Examples of the oxime compound include oxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.
Examples of the lactam compound include ε-caprolactam and γ-butyrolactam.
Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
Examples of the amine compound include primary amines and secondary amines, which may be aromatic amines, aliphatic amines, and alicyclic amines, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.

The blocked isocyanate compound that can be used in the photosensitive resin composition of the present invention is commercially available. For example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (or more, Nippon Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-84N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals, Inc.) ), 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 Corporation, Death Module B 1100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumidur BL3175 (above, manufactured by Sumika Bayer Urethane Co., Ltd.) etc. are preferably used can do.

<< Sensitizer >>
The photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote its decomposition in the combination with the compound represented by (A2) general formula (2). The sensitizer absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.

Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene), xanthenes (Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine oleoresin) Di, chloroflavin, acriflavine), acridones (eg, acridone, 10-butyl-2-chloroacridone, 10-butylacridone), anthraquinones (eg, anthraquinone), squaliums (eg, squalium), styryl , Base styryls (eg 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (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] quinolizine-11-non), naphthofurans, naphthopyrans, naphthothiofurans.
Among these sensitizers, polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable. Of the polynuclear aromatics, anthracene derivatives are most preferred.
In addition, compounds described in paragraphs 0083 to 0102 of JP2013-213867A can be preferably used, and the contents thereof are incorporated in the present specification.

When the photosensitive resin composition of the present invention contains a sensitizer, the addition amount of the sensitizer is preferably 0 to 1000 parts by mass with respect to 100 parts by mass of the photoacid generator of the photosensitive resin composition. The amount is more preferably 10 to 500 parts by weight, further preferably 50 to 400 parts by weight, and particularly preferably 50 to 350 parts by weight. The addition amount of the sensitizer is also preferably 50 to 200 parts by mass with respect to 100 parts by mass of the photoacid generator of the photosensitive resin composition.
A sensitizer may be used individually by 1 type, or may use 2 or more types together. When two or more kinds of sensitizers are used, the total amount is within the above range.

<< Surfactant >>
The photosensitive resin composition of the present invention may contain a surfactant. As the surfactant, any of anionic, cationic, nonionic, or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F Top (manufactured by JEMCO), Mega Fuck (manufactured by DIC Corporation), Florard (Sumitomo 3M) Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), SH-8400 (Toray Dow Corning Silicone), and the like.
In addition, the surfactant contains the structural unit A and the structural unit B represented by the following general formula (J-1), and is converted to polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. A copolymer having a weight average molecular weight (Mw) of 1,000 or more and 10,000 or less can be given as a preferred example.

General formula (J-1)

(In the formula (J-1), R ⁴⁰¹ and R ⁴⁰³ each represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or a carbon number. 1 represents an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is a numerical value of 10 mass% to 80 mass%. Q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, and s represents an integer of 1 to 10.

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

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

When the photosensitive resin composition of this invention contains surfactant, it is preferable that the addition amount of surfactant is 10 mass parts or less with respect to 100 mass parts of total solids in the photosensitive resin composition. 0.001 to 10 parts by mass is more preferable, and 0.01 to 3 parts by mass is even more preferable. Surfactant may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of surfactant, the total amount becomes the said range.

<< Antioxidant >>
The photosensitive resin composition of the present invention may contain an antioxidant. As an antioxidant, a well-known antioxidant can be included. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat-resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives. Among them, phenolic antioxidants, hindered amine antioxidants, phosphorus antioxidants, amide antioxidants, hydrazide antioxidants, sulfur oxidations are particularly preferred from the viewpoint of coloring of the cured film and reduction of the film thickness. Inhibitors are preferred. These may be used individually by 1 type and may mix 2 or more types.
Examples of commercially available phenolic antioxidants include ADK STAB AO-15, ADK STAB AO-18, ADK STAB AO-20, ADK STAB AO-23, ADK STAB AO-30, ADK STAB AO-37, ADK STAB AO-40 and ADK STAB AO. -50, ADK STAB AO-51, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-330, ADK STAB AO-412S, ADK STAB AO-503, ADK STAB A-611, ADK STAB A-612, ADK STAB A -613, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8W, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB PEP-36Z, ADK STAB HP-1 ADK STAB 2112, ADK STAB 260, ADK STAB 1522, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 13510, ADK STAB 3010, ADK STAB CDA-1, ADK STAB CDA-6, ADK STAB ZS-27, ADK STAB ZS-90 -91, ADK STAB LA-52, ADK STAB LA-81 (above, manufactured by ADEKA Corporation), Irganox 245FF, Irganox 1010FF, Irganox 1010, Irganox MD1024, Irganox 1035FF, Irganox 1035, Irganox 1098, Irganox 1330, Irganox 1520L, Irganox 3114, Irganox 1726 Irgafos 168, Irugamoddo 295, (manufactured by BASF (Ltd.)) Tinuvin 144, Santonox R (Monsanto Co., Ltd.). In addition, the compounds described in paragraphs 0108 to 0116 of JP 2011-227106 A can also be mentioned. Among these, ADK STAB AO-60, ADK STAB AO-80, Irganox 1726, Irganox 1035, and Irganox 1098 are listed.

When the composition of the present invention contains an antioxidant, the content of the antioxidant is preferably 0.1 to 10% by mass with respect to the total solid content of the photosensitive resin composition. It is more preferably from 5 to 5% by mass, particularly preferably from 0.5 to 4% by mass. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation becomes good.
As additives other than antioxidants, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like are used in the present invention. You may add to a resin composition.
Antioxidants may be used alone or in combination of two or more. When using 2 or more types of antioxidant, the total amount becomes the said range.

<< Acid Proliferator >>
In the photosensitive resin composition of the present invention, an acid proliferating agent can be used for the purpose of improving sensitivity.
The acid proliferating agent that can be used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. is there. In such a compound, since one or more acids increase in one reaction, the reaction proceeds at an accelerated rate as the reaction proceeds. However, the generated acid itself induces self-decomposition, and is generated here. The acid strength is preferably 3 or less as an acid dissociation constant, pKa, and particularly preferably 2 or less.
Specific examples of the acid proliferating agent include paragraph numbers 0203 to 0223 of JP-A-10-1508, paragraphs 0016 to 0055 of JP-A-10-282642, and page 39 of JP-T 9-512498. The compounds described on line 12 to page 47, line 2 can be mentioned, the contents of which are incorporated herein.
Examples of the acid proliferating agent that can be used in the present invention include pKa such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and phenylphosphonic acid, which are decomposed by an acid generated from the acid generator. Examples include compounds that generate 3 or less acids.
In particular

Etc.

When the composition of the present invention contains an acid proliferating agent, the content of the acid proliferating agent in the photosensitive composition is 10 to 1,000 parts by mass with respect to 100 parts by mass of the photoacid generator. It is preferable from the viewpoint of dissolution contrast between the exposed area and the unexposed area, and more preferably 20 to 500 parts by mass. The acid proliferating agent may be used alone or in combination of two or more. When two or more kinds of acid proliferating agents are used, the total amount is within the above range.

<< Development accelerator >>
The photosensitive resin composition of the present invention can contain a development accelerator.
As the development accelerator, the description in paragraphs 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.
Specifically, as the development accelerator, any compound having a development acceleration effect can be used, and the development accelerator may be a compound having at least one structure selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an alkyleneoxy group. Preferably, a compound having a carboxyl group or a phenolic hydroxyl group is more preferable, and a compound having a phenolic hydroxyl group is more preferable.
The molecular weight of the development accelerator is preferably 100 to 2000, more preferably 150 to 1500, and most preferably 150 to 1000.
Examples of development accelerators having an alkyleneoxy group include polyethylene glycol, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, polyethylene glycol glyceryl ester, polypropylene glycol glyceryl ester, polypropylene glycol diglyceryl ester, polybutylene glycol, Examples thereof include polyethylene glycol-bisphenol A ether, polypropylene glycol-bisphenol A ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, and compounds described in JP-A-9-222724.
Examples of compounds having a carboxy group include compounds described in JP-A No. 2000-66406, JP-A No. 9-6001, JP-A No. 10-20501, JP-A No. 11-338150, and the like.
Examples of those having a phenolic hydroxyl group include JP-A-2005-346024, JP-A-10-133366, JP-A-9-194415, JP-A-9-222724, JP-A-11-171810, Examples thereof include compounds described in JP 2007-121766, JP-A-9-297396, JP-A 2003-43679, and the like. Among these, phenol compounds having 2 to 10 benzene rings are preferable, and phenol compounds having 2 to 5 benzene rings are more preferable. Particularly preferred is a phenolic compound disclosed as a dissolution accelerator in JP-A-10-133366.

A development accelerator may be used individually by 1 type, and can also use 2 or more types together.
When the photosensitive resin composition of the present invention contains a development accelerator, the addition amount of the development accelerator is 0 to 30 with respect to 100 parts by mass of the total solid content of the photosensitive composition from the viewpoint of sensitivity and residual film ratio. Mass parts are preferred, 0.1 to 20 parts by mass are more preferred, and 0.5 to 10 parts by mass are even more preferred. When two or more types of development accelerators are used, the total amount is within the above range.
In addition, as other additives, thermal radical generators described in paragraphs 0120 to 0121 of JP2012-8223A, nitrogen-containing compounds and thermal acid generators described in WO2011-133604A1, can be used. Is incorporated herein by reference.

<Method for preparing photosensitive resin composition>
Each component is mixed in a predetermined ratio and by any method, stirred and dissolved to prepare a photosensitive resin composition. For example, a resin composition can be prepared by preparing a solution in which components are dissolved in a solvent in advance and then mixing them in a predetermined ratio. The composition solution prepared as described above can be used after being filtered using a filter having a pore size of 0.2 μm or the like.

(Pattern manufacturing method)
Next, the pattern manufacturing method of the present invention will be described. The pattern manufacturing method of the present invention is a method of forming a pattern on a substrate, and preferably includes the following steps (1) to (4).
(1) The process of apply | coating the photosensitive resin composition of this invention to the at least one surface of a board | substrate,
(2) a step of drying the photosensitive resin composition to form a photosensitive resin composition layer;
(3) a step of exposing the photosensitive resin composition layer;
(4) A process for producing a pattern comprising a step of developing the exposed photosensitive resin composition layer.

Furthermore, (5) a step of performing etching using the formed pattern as an etching resist, and (6) a step of removing the pattern by plasma treatment or chemical treatment may be included.
Each step will be described below in order.

In the application step (1), the photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent. Before applying the photosensitive resin resin composition to the substrate, it is preferable to perform substrate cleaning such as alkali cleaning or plasma cleaning, and it is more preferable to treat the substrate surface with hexamethyldisilazane after substrate cleaning. By performing this treatment, the adhesiveness of the photosensitive resin composition to the substrate tends to be improved. The method for treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method in which the substrate is exposed to hexamethyldisilazane 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 tantalum film, a tantalum alloy film, a tungsten film, a tungsten alloy film, and an oxide doped with tin oxide. Metal substrates such as indium (ITO, IZO) film, tin oxide film, Ni, Cu, Fe, Al, etc .; quartz (SiOx), glass, silicon nitride film, silicone, silicone nitride, polysilicon, silicone oxide, amorphous silicon film IGZO and other oxide semiconductor films, SOG, silicon substrates such as glass square substrates for manufacturing liquid crystal elements; polymer substrates such as paper, polyester film, polycarbonate film, polyimide film, and other polymer substrates used in organic EL display devices Ceramic materials, Ti substrates, Al substrates It can be used. Among them, in the present invention, an ITO substrate, a molybdenum substrate, a silicon substrate, a SiOx substrate, a SiNx substrate, a Cu substrate, or an Al substrate is preferable, and an ITO substrate, a molybdenum substrate, a SiOx substrate, a SiNx substrate, or a silicon substrate is preferable. It is more preferable that
The shape of the substrate may be a plate shape or a roll shape. Further, the thickness of the inorganic film to be etched is not limited, and may be a film having an ideographic surface of only a few nm, or the material of the whole substrate. Moreover, the case where the base-material surface is the composite surface of the said material (board | substrate) may be sufficient.
The coating method on the substrate is not particularly limited, and for example, a method such as an inkjet method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method can be used. Furthermore, it is also possible to apply a so-called pre-wet method as described in JP-A-2009-145395.
The wet film thickness when applied is not particularly limited, and can be applied with a film thickness according to the application, but it is usually used in the range of 0.5 to 10 μm.

(2) The step of drying is a step of removing the solvent by drying. More specifically, the solvent is removed from the applied film by reducing pressure (vacuum) and / or heating to form a dry coating film on the substrate. The heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are in the above ranges, the pattern adhesiveness is better and the residue tends to be further reduced.

In the exposure step (3), the substrate provided with the coating film is irradiated with actinic rays through a mask having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. Due to the catalytic action of the generated acid, the acid-decomposable group contained in the coating film component is hydrolyzed to generate a carboxyl group or a phenolic hydroxyl group.
As an exposure light source using actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, and the like can be used. Actinic rays having a wavelength of 300 nm to 450 nm, such as 405 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.
In order to accelerate the hydrolysis reaction in the region where the acid catalyst is generated, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as “PEB”) can be performed. PEB can promote the formation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The temperature for 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.
However, since the acid-decomposable group in the present invention has low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to generate a carboxyl group or a phenolic hydroxyl group, PEB is not necessarily performed. A positive image can also be formed by development.

When exposing using a mask, a halftone mask can be used in addition to a normal mask.

<Halftone phase difference mask>
The halftone (HT) phase difference mask is a mask that cancels the diffracted light to the periphery of the pattern at the time of exposure with light having an opposite phase. As the halftone (HT) phase difference mask 30, a transparent substrate 32 provided with a phase shifter portion (phase change film 31) having a specific transmittance on the outer periphery of an exposure pattern is used. An exposure mode using this is schematically shown in FIG. In FIG. 3, s indicates a transmission part, k indicates an exposure part (substrate), 33 indicates a light intensity distribution, 34 indicates a light amplitude distribution (positive phase), and 35 indicates a light amplitude distribution (reverse phase). Yes. As can be seen from this figure, according to this exposure mode, the light whose waveforms are inverted are irradiated adjacent to each other, so that the difference in the amount of light at the edge portion of the pattern is increased and the exposure resolution can be improved. A processing method employing such an exposure method is known, and for example, the procedures and conditions described in JP 2010-8868 A and JP 2007-241136 A can be referred to. The form of the halftone phase difference mask applied to the present invention is not particularly limited. For example, a laminated mask in which the phase shifter layer is divided into a transmittance adjustment layer and a phase adjustment layer may be used.
As described above, a halftone phase difference mask refers to a mask having a transmission part and a phase shifter part. In the present invention, in addition to a mask having a transmission part and a phase shifter part, a transmission part, a phase You may use the mask which has a shifter part and a light-shielding part.

In the developing step (4), a copolymer having a liberated carboxyl group or phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing an exposed area containing a resin composition having an acid group that easily dissolves in an alkaline developer, such as a carboxyl group or a phenolic hydroxyl group.
The developer used in the development step preferably contains an aqueous solution of a basic compound. Examples of basic compounds include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; sodium bicarbonate, potassium bicarbonate Alkali metal bicarbonates such as: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, diethyldimethylammonium hydroxide, and other tetraalkylammonium hydroxides: Alkyl) trialkylammonium hydroxides; silicates such as sodium silicate and sodium metasilicate; ethylamine, propylamine, diethylamine, triethylammonium Alkylamines such as diamine; alcohol amines such as dimethylethanolamine and triethanolamine; 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0 ] Cycloaliphatic amines such as -5-nonene can be used.
Of these, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide) are preferable.
An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.

The pH of the developer is preferably from 9.0 to 15.0, more preferably from 10.0 to 14.0. The concentration of the developer is preferably from 0.1 to 20% by mass, more preferably from 0.1 to 5.0% by mass.
The development time is preferably 30 to 180 seconds, and the development method may be any of a liquid piling method, a dipping method, a shower method, and the like. After development, washing with running water can be performed for 30 to 300 seconds to form a desired pattern.
A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, a shower rinse, a dip rinse, etc. can be mentioned.

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

The pattern manufacturing method of the present invention may include (6) a step of stripping the resist pattern. There is no restriction | limiting in particular as a peeling method of the said resist pattern, A well-known method can be used. The resist pattern is preferably peeled off by plasma treatment or chemical treatment.

(Cured film)
In the present invention, (4) after the developing step, the pattern corresponding to the unexposed area obtained by development is predetermined at a predetermined temperature, for example, 100 to 250 ° C., using a heating device such as a hot plate or an oven. A cured film having excellent hardness and the like can be formed by performing the heat treatment for 5 to 60 minutes on a hot plate, and 30 to 90 minutes on an oven.
Moreover, when performing heat processing, transparency of a cured film can also be improved by performing in nitrogen atmosphere.
Prior to the heat treatment, the substrate on which the cured film is formed in a pattern can be re-exposed with actinic rays and then heated.

The exposure in the re-exposure step may be performed by the same means as in the exposure step. However, in the re-exposure step, the entire surface of the substrate on which the film is formed by the photosensitive resin composition of the present invention is used. It is preferable to perform exposure. A preferable exposure amount for the re-exposure step is 100 to 1,000 mJ / cm ² .

(pattern)
The pattern of this invention is a pattern obtained by etching the said board | substrate using the resist pattern obtained by hardening | curing the photosensitive resin composition of this invention as a mask. The pattern of the present invention is preferably ITO, molybdenum, silicon, SiOx, SiNx, Cu, or Al, and more preferably ITO, molybdenum, SiOx, SiNx, or silicon.
The photosensitive resin composition of the present invention is excellent in releasability, sensitivity, resolution, and exposure margin, and has excellent adhesion to materials on various substrate surfaces, so that a resist pattern having excellent rectangularity can be obtained. Since the pattern of the present invention is obtained by the method for producing a pattern of the present invention using the resist pattern, it can be finely processed, and an organic EL display device or a liquid crystal display device can have high definition display characteristics.

(Liquid crystal display device)
The liquid crystal display device of the present invention comprises a pattern of a functional inorganic film formed using the photosensitive resin composition of the present invention. That is, it has the pattern manufactured by the pattern manufacturing method of the present invention.
The liquid crystal display device of the present invention is not particularly limited except that it has a pattern of a functional inorganic film formed using the photosensitive resin composition of the present invention, and known liquid crystal display devices having various structures are used. Can be mentioned.
For example, specific examples of TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. 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, as a liquid crystal driving method that can be adopted by the liquid crystal display device of the present invention, a TN (Twisted Nematic) method, a VA (Virtual Alignment) method, an IPS (In-Place-Switching) method, an FFS (Frings Field Switching) method, an OCB (Optical) method. Compensated Bend) method and the like.
In the panel configuration, the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device. For example, the organic insulating film (115) of JP-A-2005-284291, -346054 can be used as the organic insulating film (212).
Specific examples of the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method. Further, the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in JP-A Nos. 2003-149647 and 2011-257734.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a micro lens provided on the color filter in the solid-state image sensor Can be suitably used.
FIG. 2 is a conceptual cross-sectional view showing an example of the active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two

glass substrates

14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
The light source of the backlight is not particularly limited, and a known light source can be used. For example, a white LED, a multicolor LED such as blue, red, and green, a fluorescent lamp (cold cathode tube), and an organic EL can be used.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. It is also possible to make it flexible.

(Touch panel display)
FIG. 4 is a conceptual diagram illustrating an example of a touch panel display device.
4 includes a lower display panel 200 corresponding to a thin film transistor display panel provided with a thin film transistor (TFT) 440, a plurality of color filters on a surface facing the lower display panel 200 and facing the lower display panel 200. 330 includes an upper display panel 300 corresponding to a color filter display panel 330 and a liquid crystal layer 400 formed between the lower display panel 200 and the upper display panel 300. The liquid crystal layer 400 includes liquid crystal molecules (not shown).

The lower display panel 200 is disposed on the first insulating substrate 210, the thin film transistor (TFT) disposed on the first insulating substrate 210, the insulating film 280 formed on the upper surface of the thin film transistor (TFT), and the insulating film 280. A pixel electrode 290 is included. The thin film transistor (TFT) may include a gate electrode 220, a gate insulating film 240 covering the gate electrode 220, a semiconductor layer 250, ohmic contact layers 260 and 262, a source electrode 270, and a drain electrode 272.
The insulating film 280 can be formed using the photosensitive resin composition of the present invention.
A contact hole 282 is formed in the insulating film 280 so that the drain electrode 272 of the thin film transistor (TFT) is exposed.

The upper display panel 300 is disposed on one surface of the second insulating substrate 310, the light shielding members 320 arranged in a matrix, the color filter 330 disposed on the second insulating substrate 310, and the color filter 330. And a common electrode 370 for applying a voltage to the liquid crystal layer 400 corresponding to the pixel electrode 290 of the lower display panel 200.

In the liquid crystal display device shown in FIG. 4, a metal mesh 410 and a protective film 420 are provided on the other surface of the second insulating substrate 310.

(Organic EL display device)
The organic EL display device of the present invention includes a functional inorganic film pattern formed using a photosensitive resin composition. That is, it has the pattern manufactured by the pattern manufacturing method of the present invention.
The organic EL display device of the present invention is not particularly limited except that it has a pattern of a functional inorganic film formed using the photosensitive resin composition, and various known organic EL display devices having various structures. And a liquid crystal display device.
For example, specific examples of TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
FIG. 1 is a conceptual diagram of an example of an organic EL display device. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening film 4 is formed on the insulating film 3 with the unevenness due to the wiring 2 being embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 1, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a first layer made of Al is formed on the entire surface above the substrate. An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it. An EL display device is obtained.

Since the photosensitive resin composition of the present invention has good pixel rectangularity, a resist pattern formed using the photosensitive resin composition of the present invention is used as a partition wall of a MEMS device. Examples of such MEMS devices include parts such as SAW filters, BAW filters, gyro sensors, display micro shutters, image sensors, electronic paper, inkjet heads, biochips, sealants, and the like. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

In the following synthesis examples, the following symbols represent the following compounds, respectively.
MAEVE: 1-ethoxyethyl methacrylate MATH: Tetrahydro-2H-furan-2-yl methacrylate PHS: parahydroxystyrene BzMA: (benzyl methacrylate) (manufactured by Wako Pure Chemical Industries, Ltd.)
MMA: Methyl methacrylate MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
HEMA: Hydroxyethyl methacrylate (Wako Pure Chemical Industries, Ltd.)
PGMEA: Propylene glycol monomethyl ether acetate V-65: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries)
V-601: Dimethyl-2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries)
HMDS: Hexamethyldisilane

(Synthesis Example 1: Synthesis of A1-1)
20 g of 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 to distill off water and PGMEA azeotropically. After confirming that the water content was sufficiently low, 24 g of ethyl vinyl ether and 0.35 g of p-toluenesulfonic acid were added and stirred at room temperature for 1 hour. Thereto, 0.28 g of triethylamine was added to stop the reaction. Ethyl acetate was added to the reaction solution, followed by washing with water, and then ethyl acetate, water and azeotropic PGMEA were distilled off by distillation under reduced pressure to obtain A1-1, an alkali-soluble resin protected with an acid-decomposable group. It was. The weight average molecular weight of the obtained resin was 20000. The polydispersity was 1.13.
The structure of A1-1 is a 1-ethoxyethyl protector of p-hydroxystyrene / p-hydroxystyrene copolymer (30 mol% / 70 mol%).
A1-1

(Synthesis Example 2: Synthesis of A1-2)
15.6 g of 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, and water and PGMEA were distilled off azeotropically. After confirming that the water content was sufficiently low, 2.7 g of 2,3-dihydrofuran and 0.015 g of p-toluenesulfonic acid were added and stirred at room temperature for 2 hours. Thereto was added 0.090 g of triethylamine to stop the reaction. Ethyl acetate was added to the reaction solution, and the mixture was further washed with water. Then, ethyl acetate and water were distilled off under reduced pressure to obtain A1-2, a soluble resin having a protection rate of 25 mol%. The weight average molecular weight of the obtained resin was 12,000. The polydispersity was 1.13.
The structure of A1-2 is a 2-tetrahydrofuranyl protector of p-hydroxystyrene / p-hydroxystyrene copolymer (30 mol% / 70 mol%).
A1-2

<Synthesis of A2-1>
A2-1 copolymer was synthesized as follows.
To 144.2 parts (2 molar equivalents) of ethyl vinyl ether, 0.5 part of phenothiazine was added, and 86.1 parts (1 molar equivalent) of methacrylic acid was added dropwise while cooling the reaction system to 10 ° C. or lower. ) For 4 hours. After adding 5.0 parts of pyridinium p-toluenesulfonate, the mixture was stirred at room temperature for 2 hours and allowed to stand overnight at room temperature. To the reaction solution, 5 parts of sodium bicarbonate and 5 parts of sodium sulfate were added, and the mixture was stirred at room temperature for 1 hour. Insoluble matter was filtered and concentrated under reduced pressure at 40 ° C. or lower. .) 134.0 parts of 1-ethoxyethyl methacrylate (MAEVE) fraction of 43-45 ° C./7 mmHg was obtained as a colorless oil.
1-Ethoxyethyl methacrylate (63.28 parts (0.4 molar equivalent)), BzMA (52.83 parts (0.3 molar equivalent)), MAA (8.61 parts (0.1 molar equivalent) )), HEMA (26.03 parts (0.2 molar equivalent)) and PGMEA (110.8 parts) were heated to 70 ° C. under a nitrogen stream. While stirring this mixed solution, a mixed solution of radical polymerization initiator V-65 (trade name, manufactured by Wako Pure Chemical Industries, Ltd., 4 parts) and PGMEA (100.0 parts) was added dropwise over 2.5 hours. did. After completion of the dropping, the reaction was carried out at 70 ° C. for 4 hours to obtain an EDM solution of polymer (solid content concentration: 40%).
The weight average molecular weight of the obtained A2-1 measured by gel permeation chromatography (GPC) was 15,000.
A2-1

(Synthesis of MATHF)
Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C., and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring for 1 hour, saturated sodium bicarbonate (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, insolubles were filtered and concentrated under reduced pressure at 40 ° C. or lower to give a residual yellow oily product. Distillation under reduced pressure afforded 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) as a colorless oily substance (yield 80%) at a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg.

<Synthesis of other polymers>
Other copolymers were synthesized in the same manner as the synthesis of the polymer A2-1 except that the monomers used and the amounts used were changed to those shown in the following table. In the table, the unit is a molar ratio.

(Preparation of photosensitive resin composition)
Each component was dissolved and mixed in a solvent (PGMEA) so as to have the composition shown in the following table so that the solid concentration was 18% by mass for spin coating and 12% by mass for slit coating. It filtered with the filter made from a 2 micrometer polytetrafluoroethylene, and obtained the photosensitive resin composition of an Example and a comparative example. The blending ratio was as shown in the following table. Here, (A) the polymer component indicates the blending ratio of polymer 1 and polymer 2 (unit: mass%), and the components (B) to (E) and (L) are the above (A) polymer component The amount (parts by mass) relative to 100 parts by mass is shown.

(Photoacid generator)
B1: Compound having the following structure

B2: Compound having the following structure

<Synthesis of B2>
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 ° C. for 2 hours. I let you. Under ice-cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added for liquid separation. Potassium carbonate (19.2 g) was added to the organic layer, reacted at 40 ° C. for 1 hour, 2N HCl aqueous solution (60 mL) was added and separated, and the organic layer was concentrated, and the crystals were diluted with diisopropyl ether (10 mL). The slurry was reslurried, filtered and dried to obtain a ketone compound (6.5 g).
Acetic acid (7.3 g) and a 50 mass% aqueous hydroxylamine solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (30 mL), and the mixture was heated to reflux. After allowing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).
The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the temperature was raised to room temperature. Reacted for hours. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, then reslurried with methanol (20 mL), filtered and dried to obtain the B2 compound (the above structure) (2.3 g).
The ¹ H-NMR spectrum (300 MHz, CDCl 3) of B2 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d , 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (q, 1H), 2. 4 (s, 3H), 1.7 (d, 3H).

(Alicyclic epoxy compound)
C1 to C4: Compounds having the following structures

(Basic compound)
D1 to D2: Compounds having the following structures

D2: 1,5-diazabicyclo [4,3,0] -5-nonene (manufactured by Tokyo Chemical Industry Co., Ltd.)

(Azole compound)
E-1: 2-Mercaptobenzimidazole (the following structure)
E-5: 2-mercaptothiazoline (the following structure)
E-7: 3-amino-5-mercaptotriazole (the following structure)

(Crosslinking agent): Non-alicyclic epoxy compound F1: JER157S65 (manufactured by Mitsubishi Chemical Holdings Corporation)
F2: Denacor EX-321L (manufactured by Nagase ChemteX Corporation)

(Sensitizer)
G1 to G7: Compounds having the following structures

(Development accelerator)
L1 to L4: Compounds having the following structures

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

<Evaluation of line width stability>
Each photosensitive resin composition was spin-coated on a cleaned and HMDS-treated 550 mm × 650 mm glass substrate, prebaked on a hot plate (95 ° C. × 140 seconds), and then MPA 5500CF (extra-high pressure mercury manufactured by Canon Inc.) And a 10 μm line-and-space pattern was exposed at an exposure amount of exactly 10 μm through a predetermined mask. Thereafter, development is performed with an alkaline aqueous solution to prepare 10 substrates with such a line-and-space pattern, 10 points for each substrate, 10 μm line using an optical measuring instrument ZYGO New View 7200 (manufactured by ZYGO Corp.). The width was measured, and the standard deviation (σ) of the total measured line width of 100 points was calculated. The evaluation criteria are as follows, and 3 or more are practical levels.
1: Standard deviation σ is 0.4 μm or more 2: Standard deviation σ is 0.25 μm or more and less than 0.4 μm 3: Standard deviation σ is 0.15 μm or more and less than 0.25 μm 4: Standard deviation σ is 0.1 μm or more , Less than 0.15 μm 5: standard deviation σ is less than 0.1 μm

<Evaluation of sensitivity>
Each photosensitive resin composition is slit-coated on a cleaned, HMDS-treated glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), and then pre-baked on a hot plate at 95 ° C. for 140 seconds to remove the solvent. The photosensitive resin composition layer having a film thickness of 1.3 μm was formed by volatilization.
Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using MPA 5500CF (extra high pressure mercury lamp) manufactured by Canon Inc. The exposed photosensitive resin composition layer was developed with an alkali developer (0.4 mass% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
The sensitivity was evaluated with the exposure amount at which the 10 μm line-and-space pattern was exactly 10 μm by these operations as the optimum exposure amount. Three or more are practical levels.
1: 50mJ / cm ² or more exposure quantity required ^2: 20mJ / cm 2 or more 50 mJ / cm ² less than the exposure amount required 3: 15mJ / cm ² or more 20 mJ / cm ² less than the exposure amount required 4: 10 mJ / cm ² or more 15 mJ / cm ² less than the exposure amount 5: 10 mJ / cm ² less than the exposure

<Evaluation of peelability>
A substrate with a line and space pattern prepared in the same manner as the sensitivity evaluation was post-baked on a hot plate at 140 ° C. for 3 minutes, and then immersed in a resist stripping solution N321 (manufactured by Nagase ChemteX) heated to 40 ° C. A peelability test was performed by confirming that the resist pattern was peeled after time, and evaluated according to the following criteria.
1: A remaining film can be confirmed after immersion for 10 minutes.
2: The remaining film can be confirmed after immersion for 5 minutes, but the remaining film cannot be confirmed after immersion for 10 minutes.
3: A residual film can be confirmed after immersion for 3 minutes, but a residual film cannot be confirmed after immersion for 5 minutes.
4: A residual film can be confirmed after 2 minutes of immersion, but no residual film can be confirmed after 3 minutes of immersion.
5: No remaining film can be confirmed after immersion for 2 minutes.

As shown in the table above, the photosensitive resin composition of each example was evaluated for any of sensitivity, line width stability, and peelability in comparison with the photosensitive resin composition of each comparative example. It was found that excellent results were obtained.
When no alicyclic epoxy compound was contained (Comparative Example 1), it was found that the line width stability was remarkably inferior.
When content of an alicyclic epoxy compound exceeded 5 mass% (comparative examples 2 and 3), it turned out that peelability and a sensitivity are remarkably inferior to an Example.
It can also be seen that the peelability is significantly inferior to that of the examples when the polymer having the structural unit (a1) represented by the general formula (1) is not contained (Comparative Examples 4 to 8).
Further, when an epoxy compound other than the alicyclic epoxy compound was used (Comparative Examples 9 and 10), the line width stability was significantly inferior.

(Example 101)
<Organic EL display device>
An organic EL display device having an ITO pattern was produced by the following method (see FIG. 1).
A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. . The wiring 2 is used to connect the TFT 1 with an organic EL element formed between TFTs 1 or in a later process.

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

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

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

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

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

(Example 102)
<Liquid crystal display device>
A liquid crystal display device having an ITO pattern was produced by the following method.
In the active matrix type liquid crystal display device shown in FIG. 1 of Japanese Patent No. 332003, the pixel electrode 4 was formed using the photosensitive resin composition of Example 1 as a mask to obtain the liquid crystal display device of Example 102.
That is, the pixel electrode 4 was formed by the same method as the method for forming the first electrode 5 of the organic EL display device in Example 101.

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

1: TFT (Thin Film Transistor)
2: Wiring 3: Insulating film 4: Flattened film 5: First electrode 6: Glass substrate 7: Contact hole 8: Insulating film 10: Liquid crystal display device 12: Backlight unit 14, 15: Glass substrate 16: TFT
17: Cured film 18: Contact hole 19: ITO transparent electrode 20: Liquid crystal 22: Color filter 30: Halftone mask 32: Transparent base material 31: Phase shifter part (phase change film)
33, 34, 35: Exposure intensity curve s: Transmission part k: Exposure part (substrate)
33: Light intensity distribution 34: Light amplitude distribution (positive phase)
35: Light amplitude distribution (antiphase)
200: lower display panel 210: insulating substrate 220: gate electrode 240: gate insulating film 250: semiconductor layer 260: ohmic contact layer 270: source electrode 272: drain electrode 280: insulating film 282: contact hole 290: pixel electrode 300: upper part Display board 310: Insulating substrate 320: Light shielding member 330: Color filter 370: Common electrode 400: Liquid crystal layer 410: Metal mesh 420: Protective film 440: TFT (thin film transistor)

Claims

(A1) a polymer containing the structural unit (a1) represented by the following general formula (1), (B) a photoacid generator having a molar extinction coefficient of 500 or more in light having a wavelength of 365 nm, and (C) an alicyclic ring A photosensitive resin composition containing 0.01 to 5% by mass of an epoxy compound of the formula with respect to the total solid content;
General formula (1)

In general formula (1), R 1 and R 2 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 1 and R 2 is an alkyl group or an aryl group, and R 3 is an alkyl group or Represents an aryl group, and R 1 or R 2 and R 3 may be linked to form a cyclic ether, and R 4 represents a hydrogen atom or a methyl group.
(C) The photosensitive resin composition of Claim 1 whose alicyclic epoxy compound is a compound represented by the following general formula (I);
Formula (I)

In the general formula (I), n represents an integer of 1 to 4; R represents an organic group having 1 to 15 carbon atoms.
R in the general formula (I) is a hydrocarbon group or a group consisting of a hydrocarbon group and at least one combination of a silyl group, —O—, —CO—, —S— and —NR 1 —. The photosensitive resin composition according to claim 2, wherein R 1 represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms.
(C) The photosensitive resin composition of Claim 1 whose alicyclic epoxy compound is a compound represented by the following general formula (II);
Formula (II)

In the general formula (II), R 2 represents an organic group having 1 to 15 carbon atoms.
(C) The photosensitive resin composition of Claim 1 whose alicyclic epoxy compound is a compound represented by the following general formula (III);
Formula (III)

In general formula (III), R 3 represents an organic group having 1 to 14 carbon atoms.
(A1) The photosensitive resin composition according to any one of claims 1 to 5, wherein the polymer further comprises a structural unit (a4) represented by the following general formula (5);
General formula (5)

In general formula (5), R 4 is a hydrogen atom or a methyl group.
The photosensitive resin composition according to any one of claims 1 to 6, further comprising a polymer (A2) having a structural unit (a2) represented by the following general formula (2):
General formula (2)

In general formula (2), R 1 and R 2 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 1 and R 2 is an alkyl group or an aryl group, and R 3 is an alkyl group R 1 or R 2 and R 3 may be linked to form a cyclic ether, R 4 represents a hydrogen atom or a methyl group, and X 0 represents a single bond or an arylene group. To express.
The photosensitive resin composition according to any one of claims 1 to 7, wherein the content of (C) the alicyclic epoxy compound is 0.05 to 3 mass% with respect to the total solid content.
The photosensitive resin composition according to claim 1, further comprising (D) a basic compound.
(D) The photosensitive resin composition of Claim 9 whose basic compound is a compound represented by following General formula (4);
General formula (4)

In general formula (4), R 1 represents a group containing at least one nitrogen atom, A represents a divalent linking group, and R 2 represents an organic group.
The photosensitive resin composition according to any one of claims 1 to 10, further comprising (E) an azole compound.
The photosensitive resin composition according to claim 11, wherein the (E) azole compound is one or more selected from the following general formulas (X1) to (X5):

In the formula, X represents CR x1 R X2 , NR x3 , O, or S;
Y and Z each independently represent CR x4 or N;
R 1 , R 2 , R X1 , R X2 , R X3 and R X4 each independently represent a hydrogen atom, a mercapto group, an amino group or an alkyl group,
R 4 represents an alkyl group, a mercapto group, an amino group, an alkoxy group, or an aralkyl group,
m represents an integer of 0 to 4, and when m is 2 or more, each R 4 may be the same or different;
At least one of X, Y and Z represents NR x3 or N.
(1) a step of applying the photosensitive resin composition according to any one of claims 1 to 12 to at least one surface of a substrate;
(2) a step of drying the photosensitive resin composition to form a photosensitive resin composition layer;
(3) a step of exposing the photosensitive resin composition layer;
(4) A process for producing a pattern comprising a step of developing the exposed photosensitive resin composition layer.
Furthermore, (5) The process of etching using the formed pattern as an etching resist, and (6) The process of removing a pattern by a plasma process or a chemical | medical process, The manufacturing of the pattern of Claim 13 Method.
A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 12.
The manufacturing method of an organic electroluminescence display containing the manufacturing method of the pattern of Claim 13 or 14.
The manufacturing method of the liquid crystal display device containing the manufacturing method of the pattern of Claim 13 or 14.