JPWO2014156873A1 - Photosensitive resin composition, method for producing cured film, cured film, organic EL display device and liquid crystal display device - Google Patents

Abstract

Excellent chemical resistance in the state of a cured film, can further suppress panel display unevenness of the display device when incorporated in a liquid crystal display device etc. as a cured film, as well as high temperature, high humidity, high pressure, etc. Provided is a photosensitive resin composition capable of suppressing panel display unevenness even when exposed to harsh conditions. (A) (a1) a polymer having a structural unit having an acid group and (a2) a structural unit having a crosslinkable group, (B) a quinonediazide compound, (C) at least one nitrogen-containing heterocyclic compound, and (D ) Containing a solvent, wherein the nitrogen-containing heterocyclic compound contains two or more nitrogen-containing aromatic rings, and at least two of the nitrogen-containing aromatic rings are condensed or directly connected, and the nitrogen-containing aromatic ring is condensed The photosensitive resin composition which contains the structure of following formula (c-1) or the structure of following formula (c-2) in the structure which is directly connected. In formula (c-1) or formula (c-2), * represents a binding site with another atom.

Description

The present invention relates to a photosensitive resin composition (hereinafter also referred to as “the composition of the present invention”). Moreover, it is related with the manufacturing method of the cured film using the said photosensitive resin composition, the cured film formed by hardening | curing the photosensitive composition, and various image display apparatuses using the said cured film.
More specifically, a photosensitive resin composition suitable for forming a planarizing film, a protective film, and an interlayer insulating film of an electronic component such as a liquid crystal display device, an organic EL display device, an integrated circuit element, and a solid-state imaging device, and the use thereof The present invention relates to a method for producing a cured film.

  Organic EL display devices, liquid crystal display devices, and the like are provided with a patterned interlayer insulating film. In forming this interlayer insulating film, a photosensitive resin composition is widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained (for example, patents). Literatures 1-2).

JP-A-5-165214 JP-A-11-223937

  Here, Patent Document 2 proposes a positive photosensitive resin composition using a nitrogen-containing heterocyclic compound having a specific structure. However, the inventors of the present application have examined a resist used after forming a cured film. Inferior resistance to the solvent used for the stripping solution and interlayer insulation film, panel display unevenness when incorporated into a liquid crystal display device as a cured film, and severe conditions such as high temperature, high humidity, and high pressure It was found that panel display unevenness was likely to occur under certain conditions.

  Since the interlayer insulating film is exposed to a resist stripping solution used for forming a pattern of the transparent electrode film after the interlayer insulating film is formed and a chemical used for forming the liquid crystal alignment film, these interlayer insulating films are used. Sufficient resistance to common chemicals used in the field is required. In addition, panel display unevenness in panel evaluation under normal environmental conditions is required to suppress panel display unevenness even when exposed to severe conditions such as high temperature, high humidity, and high pressure.

  The present invention aims to solve the above-mentioned problems, and is excellent in chemical resistance in the state when it is used as a cured film, and is a panel display of a display device when incorporated in a liquid crystal display device or the like as a cured film. An object of the present invention is to provide a photosensitive resin composition that can further suppress unevenness and suppress panel display unevenness even when exposed to severe conditions such as high temperature, high humidity, and high pressure. Furthermore, it aims at providing the manufacturing method of a cured film using such a photosensitive resin composition, a cured film, an organic electroluminescence display, and a liquid crystal display device.

Under such circumstances, the inventors of the present application have made extensive studies, and as a result, the photosensitive resin composition contains a polymer containing a structural unit having an acid group and a structural unit having a crosslinkable group, and a nitrogen-containing heterocycle having a specific structure. By using the compound, the chemical resistance when the photosensitive resin composition is used for an interlayer insulating film is improved, and the panel display unevenness in the display device can be suppressed, such as high temperature, high humidity, and high pressure. It has been found that even when exposed to harsh conditions, panel display unevenness can be suppressed, and the present invention has been completed.
The reason for this is presumed, but the nitrogen-containing heterocyclic compound having a specific structure promotes crosslinking of the crosslinkable group in the photosensitive resin composition during post-baking, and forms a strong cured film having a high crosslinking density. Therefore, it is estimated that the cured film has high chemical resistance and can suppress panel display unevenness of the display device. In addition, the crosslinkable group in the photosensitive resin composition and the nitrogen-containing heterocyclic compound with a specific structure more effectively capture the decomposition products generated in the cured film under severe conditions such as high temperature, high humidity, and high pressure. Therefore, it is estimated that the panel display unevenness can be further suppressed even when exposed to severe conditions such as high temperature, high humidity, and high pressure.
Specifically, the above problem has been solved by the following means <1>, preferably <2> to <15>.
<1> (A) (a1) a polymer having a structural unit having an acid group and (a2) a structural unit having a crosslinkable group,
(B) a quinonediazide compound,
(C) at least one nitrogen-containing heterocyclic compound, and (D) a solvent,
The nitrogen-containing heterocyclic compound contains two or more nitrogen-containing aromatic rings, of which two nitrogen-containing aromatic rings are condensed or directly connected, and the nitrogen-containing aromatic ring is condensed or directly connected. The photosensitive resin composition which contains the structure of following formula (c-1) or the structure of following formula (c-2) in the structure which is.
(In the formula (c-1) or the formula (c-2), * represents a bonding site with another atom.)
<2> The above (C) wherein at least one nitrogen-containing heterocyclic compound is at least one selected from nitrogen-containing heterocyclic compounds represented by the following general formulas (1) to (3), <1> The photosensitive resin composition as described.
(In the general formula (1), R ¹ and R ² each represent a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an amino group, a halogen atom, or a mercapto group. In general formula (2), R ^{3 to} R ⁵ each represent a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an amino group, a halogen atom, or a mercapto group, and q is 0. And r and s each represent an integer of 0 to 3. In general formula (3), R ⁶ and R ⁷ are each a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, or an alkyl group. Represents an amino group, a halogen atom or a mercapto group, and t and u each represents an integer of 0 to 4.)
<3> The (C) at least one nitrogen-containing heterocyclic compound is a nitrogen-containing heterocyclic compound represented by the following general formula (1-1), the general formula (2), or the general formula (3). The photosensitive resin composition according to <2>, which is at least one selected.
(In the general formula (1-1), R ¹¹ and R ²¹ each represent a hydrogen atom, a hydroxyl group, a sulfonic acid group or an alkyl group. X ¹ represents a hydrogen atom, an acyl group or an alkyl group. P1 represents Represents an integer of 0 to 2.)
<4> The nitrogen heterocyclic compound is 4-hydroxypteridine, 2-ethyl-4-hydroxypteridine, 1,10-phenanthroline, 5-methyl-1,10-phenanthroline, 2,2′-bipyridine and 5,5. The photosensitive resin composition according to any one of <1> to <3>, which is at least one of '-dimethyl-2,2'-bipyridine.
<5> The photosensitive resin composition according to any one of <1> to <4>, wherein the structural unit (a1) is a structural unit having a carboxyl group and / or a phenolic hydroxyl group.
<6> From the group consisting of the group represented by the structural unit (a2) represented by an epoxy group, an oxetanyl group, and —NH—CH ₂ —O—R (wherein R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). The photosensitive resin composition in any one of <1>-<5> containing the structural unit containing at least 1 chosen.
<7> The photosensitive composition according to any one of <1> to <6>, wherein the blending amount of the (B) quinonediazide compound is 10 to 50 parts by mass with respect to a total of 100 parts by mass of the (A) polymer component. Resin composition.
<8> The photosensitive resin composition according to any one of <1> to <7>, wherein the polymer (A) contains a structural unit derived from (meth) acrylic acid.
<9> The photosensitive resin composition according to any one of <1> to <8>, which is a positive type.
<10> (1) The process of apply | coating the photosensitive resin composition in any one of <1>-<9> on a board | substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays,
(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) a post-baking step of thermosetting the developed photosensitive resin composition;
The manufacturing method of the cured film containing this.
<11> The method for producing a cured film according to <10>, including (6) a step of exposing the entire surface of the developed photosensitive resin composition after the development step and before the post-baking step.
<12> The method for producing a cured film according to <10> or <11>, including a step of performing dry etching on a substrate having a cured film obtained by thermosetting in the post-baking step.
<13> By the manufacturing method of the cured film formed by hardening | curing the photosensitive resin composition in any one of <1>-<9>, or the cured film in any one of <10>-<12>. Formed cured film.
<14> The cured film according to <13>, which is an interlayer insulating film.
<15> An organic EL display device or a liquid crystal display device having the cured film according to <13> or <14>.

  According to the present invention, it is excellent in chemical resistance in the state when it is used as a cured film, and when it is incorporated in a liquid crystal display device or the like as a cured film, it can further suppress panel display unevenness of the display device, Even when exposed to severe conditions such as high humidity and high pressure, a photosensitive resin composition capable of further suppressing panel display unevenness can be provided.

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

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

The photosensitive resin composition of the present invention is preferably used as a positive photosensitive resin composition.
The photosensitive resin composition of the present invention is
(A) (a1) a polymer having a structural unit having an acid group and (a2) a structural unit having a crosslinkable group,
(B) a quinonediazide compound,
(C) at least one nitrogen-containing heterocyclic compound, and (D) a solvent,
The nitrogen-containing heterocyclic compound contains two or more nitrogen-containing aromatic rings, and at least two of the nitrogen-containing aromatic rings are condensed or directly connected, and the nitrogen-containing aromatic ring is condensed or directly connected. The photosensitive resin composition which contains the structure of following formula (c-1) or the structure of following formula (c-2) in the structure which is.
(In the formula (c-1) or the formula (c-2), * represents a bonding site with another atom.)

  According to the present invention, the chemical resistance in a state of being a cured film (for example, a resist stripping solution used for forming a pattern of a transparent electrode film after forming an interlayer insulating film or a liquid crystal alignment film is used. Resistance to NMP (N-methylpyrrolidone), and can suppress panel display unevenness of a display device when incorporated in a liquid crystal display device as a cured film, and is severe such as high temperature, high humidity, and high pressure. The photosensitive resin composition which can suppress a panel display nonuniformity more even if exposed to various conditions can be provided.

<(A) Polymer>
The (A) polymer used in the present invention is a polymer containing (a1) a structural unit having an acid group and (a2) a structural unit having a crosslinkable group. (A) A polymer component becomes a main component of the component except the solvent of the composition of this invention, and it is preferable to occupy 30 mass% or more of a total solid.
Moreover, it is preferable that the (A) polymer used by this invention contains the structural unit derived from (meth) acrylic acid. Examples of the structural unit derived from (meth) acrylic acid include a structural unit derived from styrene, a structural unit derived from a vinyl compound, and a structural unit derived from (meth) acrylic acid and / or an ester thereof. And

<< (a1) Structural Unit Having Acid Group >>
By including (a1) the structural unit having an acid group in the polymer component (A), the polymer component is easily dissolved in an alkaline developer, and the effects of the present invention are more effectively exhibited. The acid group is usually incorporated into the polymer as a structural unit having an acid group using a monomer capable of forming an acid group. By including such a structural unit having an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer.
Examples of the acid group used in the present invention include a structural unit derived from a carboxylic acid group, a phenolic hydroxyl group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, and a sulfonylimide group, and the carboxylic acid group and / or phenol. A structural unit derived from a functional hydroxyl group is more preferred. In particular, the structural unit (a1) having an acid group used in the present invention is preferably a structural unit having a carboxyl group and / or a phenolic hydroxyl group. For example, the compounds described in JP-A-2012-88459, paragraph numbers 0021 to 0023 and paragraph numbers 0029 to 0044 can be used, the contents of which are incorporated herein.
The structural unit having an acid group used in the present invention is 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. For example, the compounds described in JP-A-2012-88459, paragraph numbers 0021 to 0023 and paragraph numbers 0029 to 0044 can be used, the contents of which are incorporated herein.

  Among these, acrylic acid, methacrylic acid, maleic anhydride, 4-hydroxyphenyl methacrylate, o-hydroxystyrene, p-hydroxystyrene, α-methyl-p-hydroxystyrene, etc. are copolymerized and soluble in an aqueous alkali solution. It is more preferable from the viewpoint of availability and availability. These compounds may be used alone or in combination of two or more.

  (A) Among all the structural units of the polymer component, the structural unit (a1) is preferably contained in an amount of 3 to 70 mol%, more preferably 5 to 60 mol%, and more preferably 10 to 50 mol%. More preferably, it is contained. By setting the use ratio of the structural unit (a1) within the above range, the solubility of the polymer component (A) in the alkaline aqueous solution is optimized, and a radiation-sensitive resin composition having excellent sensitivity is obtained.

<< (a2) Structural Unit Having Crosslinkable Group >>
(A) The polymer has a structural unit (a2) having a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a group that causes a curing reaction by heat treatment. As a preferable embodiment of the structural unit having a crosslinkable group, an epoxy group, an oxetanyl group, a group represented by —NH—CH ₂ —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) and ethylene. And a structural unit containing at least one selected from the group consisting of an unsaturated group, an epoxy group, an oxetanyl group, and NH—CH ₂ —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). It is preferably at least one selected from the group represented by In more detail, the following are mentioned.

<<< (a2-1) Structural Unit Having Epoxy Group and / or Oxetanyl Group >>>
The polymer (A) preferably contains a structural unit (a2-1) having an epoxy group and / or an oxetanyl group.
Specific examples of the radical polymerizable monomer used to form the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, and glycidyl α-n-propyl acrylate. Glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexyl methacrylate Methyl, α-ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, described in paragraph Nos. 0031 to 0035 of Japanese Patent No. 4168443 Alicyclic And compounds containing epoxy backbone can be cited, the contents of which are incorporated herein.
Specific examples of the radical polymerizable monomer used for forming the structural unit having an oxetanyl group include (meth) having an oxetanyl group described in paragraph Nos. 0011 to 0016 of JP-A No. 2001-330953, for example. Examples thereof include acrylate esters and compounds described in paragraph No. 0027 of JP2012-088459A, the contents of which are incorporated herein.
Specific examples of the radical polymerizable monomer used to form the structural unit (a2-1) having the epoxy group and / or oxetanyl group include a monomer containing a methacrylic ester structure and an acrylic ester structure. It is preferable that it is a monomer to contain.

  Among these, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl are preferred. Ether, acrylic acid (3-ethyloxetane-3-yl) methyl, and methacrylic acid (3-ethyloxetane-3-yl) methyl are preferred from the viewpoints of copolymerization reactivity and improved properties of the cured film. These structural units can be used individually by 1 type or in combination of 2 or more types.

  Preferable specific examples of the structural unit (a2-1) having the epoxy group and / or oxetanyl group include the following structural units. R represents a hydrogen atom or a methyl group.

<<< (a2-2) Structural unit having an ethylenically unsaturated group >>>
Examples of the structural unit (a2) having the crosslinkable group include a structural unit (a2-2) having an ethylenically unsaturated group. As said structural unit (a2-2), the structural unit which has an ethylenically unsaturated group in a side chain is preferable, and the structural unit which has an ethylenically unsaturated group at the terminal and has a C3-C16 side chain is More preferred.
In addition, examples of the structural unit (a2-2) include compounds described in paragraphs 0013 to 0031 of JP-A-2008-256974, and the contents thereof are incorporated herein.

<<< constituent unit having a group represented by (a2-3) -NH—CH ₂ —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) >>
As the structural unit (a2) having a crosslinkable group, a structural unit (a2-3) having a group represented by —NH—CH ₂ —O—R (where R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). Is also preferred. By having the structural unit (a2-3), a curing reaction can be caused by a mild heat treatment, and a cured film having excellent characteristics can be obtained. Here, R is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group. The structural unit (a2-3) is more preferably a structural unit having a group represented by the following general formula (a2-30).
Formula (a2-30)
(In general formula (a2-30), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)
R ² is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
Specific examples of R ² include a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, i-butyl, n-butyl and methyl are preferred.

  (A) It is preferable that 20-80 mol% of structural units (a2) are contained in all the structural units of a polymer component, it is more preferable that 20-70 mol% is contained, 20-65 mol%. More preferably it is contained. By setting the use ratio of the structural unit (a2) within the above range, a cured film having excellent characteristics can be formed.

<< (a3) Other structural units >>
In the present invention, the polymer (A) may have another structural unit (a3) in addition to the structural units (a1) and (a2). The monomer that becomes the other structural unit (a3) is not particularly limited as long as it is an unsaturated compound other than the structural units (a1) and (a2). Specific examples of the radical polymerizable monomer used for forming the structural unit (a3) include, for example, a methacrylic acid chain alkyl ester, a methacrylic acid cyclic alkyl ester, an acrylic acid chain alkyl ester, and an acrylic acid cyclic alkyl ester. Methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, bicyclo unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton, Examples thereof include unsaturated compounds containing the skeleton represented by 4) and other unsaturated compounds. As specific examples of the radical polymerizable monomer used for forming the structural unit (a3), compounds described in paragraph Nos. 0046 to 0065 of JP 2012-88459 A, and the like can be used. It is incorporated herein.

In the formula (4), R ²³ is a hydrogen atom or a methyl group. s is an integer of 1 or more.

  Among these structural units (a3), a methacrylic acid chain alkyl ester, a methacrylic acid cyclic alkyl ester, a maleimide compound, a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, and a skeleton represented by the above formula (4) An unsaturated compound, an unsaturated aromatic compound, an acrylic acid cyclic alkyl ester, and acryloylmorpholine are preferable. Among these, styrene, methyl methacrylate, t-butyl methacrylate, n-lauryl methacrylate, tricyclo [5.2.1.02,6] decan-8-yl methacrylate, p-methoxystyrene, 2-methyl Cyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol (n = 2 to 10) mono (meth) acrylate, 3- (meth) acryloyloxytetrahydrofuran-2-one, acryloyl Morpholine is more preferable from the viewpoints of copolymerization reactivity and solubility in an aqueous alkali solution. These (a3) compounds may be used alone or in admixture of two or more.

  (A) It is preferable that 1-90 mol% of structural units (a3) are contained in all the structural units of a polymer component, It is more preferable that 5-80 mol% is contained, 7-60 mol% More preferably, it is contained. By setting the use ratio of the structural unit (a3) in the above range, a cured film having excellent characteristics can be formed.

<< (A) Molecular Weight of Polymer >>
(A) The molecular weight of a polymer is a polystyrene conversion weight average molecular weight, Preferably it is 1,000-200,000, More preferably, it is the range of 2,000-50,000. Various characteristics are favorable in the range of said numerical value.
The ratio (dispersity) between the number average molecular weight and the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.

<< (A) Polymer Production Method >>
Various methods for synthesizing the component (A) are known. To give an example, the component (A) is used to form at least the structural units represented by (a1) and (a2). It can be synthesized by polymerizing a radical polymerizable monomer mixture containing a radical polymerizable monomer in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.
Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4 Azo compounds such as -methoxy-2,4-dimethylvaleronitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1'-bis- (t-butylperoxy) cyclohexane, and Examples include hydrogen peroxide.
(A) The manufacturing method of a polymer can use the method of the paragraph numbers 0067-0073 of Unexamined-Japanese-Patent No. 2012-88549, for example, This content is integrated in this-application specification.

<(B) Quinonediazide compound>
As the (B) quinonediazide compound used in the composition of the present invention, for example, a 1,2-quinonediazide compound that generates a carboxylic acid by irradiation with actinic rays can be used. As the 1,2-quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide can be used. As specific examples of these compounds, for example, description of paragraphs 0075 to 0078 of JP2012-088459A can be referred to, and the contents thereof are incorporated in the present specification.

  In the condensation reaction of the phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazidesulfonic acid halide, preferably 30 to 85 moles relative to the number of OH groups in the phenolic compound or alcoholic compound. %, More preferably 1,2-naphthoquinonediazidesulfonic acid halide corresponding to 50 to 70 mol% can be used. The condensation reaction can be carried out by a known method.

  Examples of the 1,2-quinonediazide compound include 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, for example, 2,3,4-triaminobenzophenone-1,2. -Naphthoquinonediazide-4-sulfonic acid amide etc. are also used suitably.

These (B) quinonediazide compounds can be used alone or in combination of two or more. The blending amount of the (B) quinonediazide compound in the photosensitive resin composition of the present invention is preferably 1 to 50% by mass, more than 10% by mass and 40% by mass or less, based on the total solid content in the photosensitive resin composition. More preferably, it is more than 12 mass% and 40 mass% or less.
Moreover, it is preferable that the compounding quantity of (B) quinonediazide compound in the photosensitive resin composition of this invention is 5-100 mass parts with respect to a total of 100 mass parts of said (A) polymer, and 10-50 masses. More preferably, it is 10-35 mass parts.
(B) By making the compounding quantity of a quinonediazide compound into the said range, the difference of the solubility of the irradiation part of the actinic ray with respect to the alkaline aqueous solution used as a developing solution and a non-irradiation part is large, patterning performance becomes favorable, and hardening obtained The solvent resistance of the film is improved.

<(C) Nitrogen-containing heterocyclic compound>
The composition of the present invention contains at least one nitrogen-containing heterocyclic compound. The nitrogen-containing heterocyclic compound contains two or more nitrogen-containing aromatic rings, and at least two of the nitrogen-containing aromatic rings are condensed or directly connected, and the nitrogen-containing aromatic ring is condensed or directly connected. In the structure, the structure of the following formula (c-1) or the structure of the following formula (c-2) is contained.
(In the formula (c-1) or the formula (c-2), * represents a bonding site with another atom.)

The chemical resistance of the cured film obtained by curing the composition of the present invention can be improved by blending at least one nitrogen-containing heterocyclic compound in the composition of the present invention. In addition, by incorporating at least one nitrogen-containing heterocyclic compound used in the present invention into the photosensitive resin composition, the composition of the present invention is incorporated into a liquid crystal display device or the like as a cured film. Panel display unevenness can be further suppressed. Furthermore, it is possible to further suppress panel display unevenness when the cured film obtained by curing the composition of the present invention is exposed to severe conditions such as high temperature, high humidity, and high pressure.
Although the reason for this is not clear, the nitrogen-containing heterocyclic compound promotes the crosslinking of the crosslinkable group in the photosensitive resin composition during post-baking, and forms a strong cured film having a high crosslinking density. Therefore, it is estimated that the chemical resistance of the cured film is high, and the panel display unevenness of the display device can be suppressed. In addition, the crosslinkable group in the photosensitive resin composition and the nitrogen-containing heterocyclic compound more effectively capture decomposition products generated in a cured film under severe conditions such as high temperature, high humidity, and high pressure. Even when exposed to severe conditions such as high temperature, high humidity, and high pressure, it is estimated that panel display unevenness can be further suppressed.

The nitrogen-containing aromatic ring of the nitrogen-containing heterocyclic compound is not particularly limited as long as it is an aromatic ring containing a nitrogen atom, but a 3- to 6-membered nitrogen-containing aromatic ring is preferable, and a 5-membered or 6-membered ring-containing aromatic ring is preferable. Nitrogen aromatic rings are preferred. Examples of the 5-membered nitrogen-containing aromatic ring include a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, and a tetrazole ring. Examples of the 6-membered nitrogen-containing aromatic ring include a pyridine ring, a pyridazine ring, a pyrimidine ring, and a pyrazine ring.
In the nitrogen-containing aromatic ring possessed by the nitrogen-containing heterocyclic compound, when at least two nitrogen-containing aromatic rings are condensed, the number of condensation of the nitrogen-containing aromatic ring is 2 or more, and 2 or 3 Is preferred. In the nitrogen-containing aromatic ring of the nitrogen-containing heterocyclic compound, when two or more nitrogen-containing aromatic rings are directly connected, the number of bonds of the nitrogen-containing aromatic ring is two or more, and two preferable.
The nitrogen-containing heterocyclic compound contains two or more of the nitrogen-containing aromatic rings, and at least two of the nitrogen-containing aromatic rings are condensed or directly connected to each other. The other ring may be any ring as long as it contains the structure of c-1) or the structure of the above formula (c-2), but the other rings are benzene ring and naphthalene. An aromatic ring selected from rings is preferred. The number of aromatic rings forming the nitrogen-containing heterocyclic compound is preferably 2 or 3 in one molecule.
The nitrogen-containing heterocyclic compound may or may not have a substituent on the nitrogen-containing aromatic ring, but preferably does not have it. As the substituent, when the substituent is bulky, it is difficult to capture a decomposition product generated in the cured film. Therefore, it is preferable to have a substituent that does not become bulky.
The substituent is not particularly limited, but is preferably a hydroxyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an amino group, a halogen atom, an acyl group or a mercapto group, and a hydroxyl group, a carboxyl group, a sulfonic acid group, an acyl group or an alkyl group. Are more preferable, an alkyl group and a hydroxyl group are more preferable, and a methyl group and a hydroxyl group are particularly preferable in that they are not bulky.
When the substituent is an alkyl group, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group and an ethyl group are more preferable.
When the substituent is a halogen atom, a chlorine atom, a bromine atom or an iodine atom is preferable.
When the substituent is an acyl group, an acyl group having 2 to 4 carbon atoms is preferred.
Although the number of substituents is not particularly limited, it is preferably 1 to 3 and more preferably 1 or 2 in one molecule of the nitrogen-containing heterocyclic compound.

The composition of the present invention preferably contains at least one selected from the nitrogen-containing heterocyclic compounds represented by the following general formulas (1) to (3).
(In the general formula (1), R ¹ and R ² each represent a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an amino group, a halogen atom, or a mercapto group. It represents an integer of 2. In general formula (2), R ^{3 to} R ⁵ each represent a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an amino group, a halogen atom, or a mercapto group, and q is R represents an integer of 0 to 2, and r and s each represent an integer of 0 to 3. In the general formula (3), R ⁶ and R ⁷ are a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, an alkyl group, respectively. A group, an amino group, a halogen atom or a mercapto group, and t and u each represents an integer of 0 to 4)

In the general formula (1), R ¹ and R ² each represent a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an amino group, a halogen atom or a mercapto group, and a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfone group An acid group, an acyl group, and an alkyl group are more preferable, and a hydrogen atom, a hydroxyl group, an alkyl group, and a sulfonic acid group are particularly preferable. Specifically, it is preferable that R ¹ represents a hydrogen atom and R ² represents an alkyl group or a hydroxyl group.
When R ¹ and R ² each represent an alkyl group, a preferred alkyl group is an alkyl group having 1 to 3 carbon atoms. Specifically, a methyl group and an ethyl group are preferable, and an ethyl group is particularly preferable.
When R ¹ and R ² each represent a halogen atom, preferred halogen atoms are a chlorine atom, a bromine atom and an iodine atom.
When R ¹ and R ² each represent an amino group, the amino group may be substituted with 1 or 2 alkyl groups having 1 to 3 carbon atoms.
When R ¹ and R ² each represent an acyl group, an acyl group having 2 to 4 carbon atoms is preferred.
In general formula (1), p and v each represent an integer of 0 to 2. When p and v represent 2, R ¹ may not be the same.

In General Formula (2), R ^{3 to} R ⁵ each represent a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an amino group, a halogen atom, or a mercapto group, and a hydrogen atom, a hydroxyl group, a carboxyl group, or a sulfone group. An acid group and an alkyl group are more preferable, and a hydrogen atom and an alkyl group are particularly preferable. Specifically, it is preferable that R ³ and R ⁵ represent a hydrogen atom and R ⁴ represents an alkyl group.
When R < ³ > -R < ⁵ > represents an alkyl group, respectively, a preferable alkyl group is a C1-C3 alkyl group. Specifically, a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.
When R ^{3 to} R ⁵ each represent a halogen atom, preferred halogen atoms are a chlorine atom, a bromine atom and an iodine atom.
When R ^{3 to} R ⁵ each represent an amino group, the amino group may be substituted with 1 or 2 alkyl groups having 1 to 2 carbon atoms.
In general formula (2), q represents the integer of 0-2. q is preferably an integer of 0 to 2. When p represents 2, R ⁴ may not be the same as each other, but is preferably the same.
In general formula (2), r and s each represent an integer of 0 to 3. r and s are each preferably an integer of 0 to 2, and more preferably 0. When r and s represent 2 or 3, R ⁴ and R ⁵ may or may not be the same as each other.

In general formula (3), R ⁶ and R ⁷ represent a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an amino group, a halogen atom or a mercapto group, respectively. More preferred are a hydrogen atom and an alkyl group. Specifically, it is preferable that R ⁶ and R ⁷ each represent a hydrogen atom or an alkyl group.
When R ⁶ and R ⁷ each represent an alkyl group, preferred alkyl groups are alkyl groups having 1 to 3 carbon atoms. Specifically, a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.
When R ⁶ and R ⁷ each represent a halogen atom, preferred halogen atoms are a chlorine atom, a bromine atom and an iodine atom.
When R ⁶ and R ⁷ each represent an amino group, the amino group may be substituted with 1 or 2 alkyl groups having 1 to 2 carbon atoms.
In general formula (3), t and u each represent an integer of 0 to 4. t and u are each preferably an integer of 0 to 2, and more preferably 0 or 1. When t and u represent an integer of 2 to 4, t and u may or may not be the same.

In at least one nitrogen-containing heterocyclic compound selected from the compounds represented by the general formulas (1) to (3), the substituents (R ^{1 to} R ⁷ ) on the aromatic ring are bulky. When it is high, it becomes difficult to capture a decomposition product generated in the cured film. Therefore, it is more preferable to have a substituent that does not have a substituent or does not become bulky. For example, a methyl group and a hydroxyl group are particularly preferable as the substituent that does not become bulky.

The nitrogen-containing heterocyclic compound represented by the general formula (1) is more preferably represented by the following general formula (1-1).
(In the general formula (1-1), R ¹¹ and R ²¹ each represent a hydrogen atom, a hydroxyl group, a sulfonic acid group or an alkyl group. X ¹ represents a hydrogen atom, an acyl group or an alkyl group. P1 represents Represents an integer of 0 to 2.)
In General Formula (1-1), R ¹¹ and R ²¹ each represent a hydrogen atom, a hydroxyl group, a sulfonic acid group, or an alkyl group. R ¹¹ and R ²¹ have the same meanings as R ¹ and R ² in the general formula (1), and preferred ranges thereof are also the same.
In general formula (1-1), X < ¹ > represents a hydrogen atom, an acyl group, or an alkyl group, and a hydrogen atom is preferable. When X ¹ represents an alkyl group, a preferred alkyl group is an alkyl group having 1 to 3 carbon atoms. Specifically, a methyl group and an ethyl group are preferable. When X ¹ represents an acyl group, an acyl group having 2 to 4 carbon atoms is preferred.
In general formula (1-1), p1 represents the integer of 0-2, is synonymous with p in the said general formula (1), and its preferable range is also the same.

  In particular, the nitrogen-containing heterocyclic compounds include 4-hydroxypteridine, 2,4-dihydroxypteridine, 4-hydroxypteridine-2-sulfonic acid, 2-ethyl-4-hydroxypteridine, 2-methyl-4-hydroxypteridine. 1,10-phenanthroline, 5-methyl-1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline, 3,8-dimethyl-1,10-phenanthroline, 3,8-dihydroxy-1,10 -Phenanthroline, 5-carboxy-1,10-phenanthroline, 5,6-dihydroxy-1,10-phenanthroline, 1,10-phenanthroline-5-sulfonic acid, 4,4'-dimethyl-2,2'-bipyridine, 2,2′-bipyridine, 2,2′-bipyridine-5-carboxylic acid, , 5'-dichloro-2,2'-bipyridine, 3,3'-dihydroxy-2,2'-bipyridine, 3,3'-dimercapto-2,2'-bipyridine, 5,5'-dimethyl-2, Although 2'- bipyridine etc. are mentioned, this invention is not limited to these. Among them, 4-hydroxypteridine, 2-ethyl-4-hydroxypteridine, 1,10-phenanthroline, 5-methyl-1,10-phenanthroline, 2,2′-bipyridine, 5,5′-dimethyl-2,2 '-Bipyridine is particularly preferred.

  Among these compounds, 4-hydroxypteridine derivatives are obtained by reacting the corresponding 4,5-diaminopyrimidine and glyoxal according to a conventional method. In addition, 1,10-phenanthroline derivatives and 2,2′-bipyridine derivatives can also be obtained by adding substituents to 1,10-phenanthroline and 2,2′-bipyridine, respectively, according to a conventional method.

  The molecular weight of the nitrogen-containing heterocyclic compound is preferably 1000 or less, more preferably 750 or less, and even more preferably 500 or less.

In the composition of this invention, it is preferable that the compounding quantity of the said nitrogen-containing heterocyclic compound is 0.001-15 mass parts with respect to a total of 100 mass parts of said (A) polymer component, 0.05- More preferably, it is 10 mass parts, and it is still more preferable that it is 0.01-5 mass parts.
1 type may be sufficient as the nitrogen-containing heterocyclic compound contained in the composition of this invention, and 2 or more types may be sufficient as it. When 2 or more types of the said nitrogen-containing heterocyclic compound are included in the composition of this invention, it is preferable that the sum total of a nitrogen-containing heterocyclic compound is the said range.

<(D) Solvent>
The photosensitive resin composition of the present invention contains (D) a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and optional components described below are dissolved in the solvent (D). As a solvent used for the preparation of the composition of the present invention, a solvent that uniformly dissolves essential components and optional components and does not react with each component is used.
As the solvent (D) used in the photosensitive resin composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene. Glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol Examples include monoalkyl ether acetates, esters, ketones, amides, lactones and the like. Moreover, as a specific example of the solvent used for the photosensitive resin composition of this invention, the solvent of paragraph number 0174-0178 of Unexamined-Japanese-Patent No. 2011-221494, paragraph number 0167-0168 of Unexamined-Japanese-Patent No. 2012-194290. And the contents thereof are incorporated herein by reference.

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

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

  The content of the (D) solvent in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass, preferably 60 to 90 parts by mass, per 100 parts by mass of all components in the photosensitive resin composition. More preferably.

<Other ingredients>
The composition of the present invention comprises, in addition to the above components, a crosslinking agent, an antioxidant, a development accelerator, an alkoxysilane compound (silane coupling agent), and a surfactant, as long as the effects of the present invention are not impaired. In addition, optional components such as an adhesion assistant, a heat resistance improver, and a heat-sensitive acid generator can be contained. These optional components may be used alone or in combination of two or more. As these compounds, for example, compounds described in paragraph Nos. 0201 to 0224 of JP2012-8859A can be used, and the contents thereof are incorporated in the present specification.

Alkoxysilane Compound The photosensitive resin composition of the present invention preferably contains an alkoxysilane compound as an adhesion improver. 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. 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 the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropyl dialkoxysilane, and γ-methacryloxy. Propyltrialkoxysilane, γ-methacryloxypropyl dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Can be 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.

Moreover, the compound represented with the following general formula can also be employ | adopted preferably.
_{^{(R 1) 4-n -Si-}} (OR 2) n
In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms having no reactive group, R ² is an alkyl group or a phenyl group having 1 to 3 carbon atoms, n represents an integer of 1 to 3 It is.
Specific examples thereof include the following compounds.

In the above, Ph is a phenyl group.

The alkoxysilane compound in the photosensitive resin composition of the present invention is not particularly limited, and known compounds can be used.
As for content of the alkoxysilane compound in the photosensitive resin composition of this invention, 0.1-30 mass parts is preferable with respect to a total of 100 mass parts of said (A) polymer component, 0.5-20 mass parts Is more preferable.

Surfactant The photosensitive resin composition of the present invention preferably contains 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 the surfactant used in the composition of the present invention include those described in paragraph numbers 0201 to 0205 of JP2012-88459A and paragraph numbers 0185 to 0188 of JP2011-215580A. Can be used and these descriptions are incorporated herein.
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. . The following trade names are KP-341, X-22-822 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 99C (manufactured by Kyoeisha Chemical Co., Ltd.), F-top (manufactured by Mitsubishi Materials Kasei Co., Ltd.), MegaFac (manufactured by DIC Corporation), Florard Novec FC-4430 (manufactured by Sumitomo 3M Corporation), Surflon S-242 (Manufactured by AGC Seimi Chemical Co., Ltd.), PolyFoxPF-6320 (manufactured by OMNOVA), SH-8400 (Toray Dow Corning Silicone), and footgent FTX-218G (manufactured by Neos).
The addition amount of the surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by mass or less, and 0.001 to 10 parts by mass with respect to 100 parts by mass in total of the polymer (A). More preferably, it is more preferably 0.01 to 5 parts by mass. A plurality of surfactants can be used in combination, and in that case, the content is calculated by adding all the surfactants.

Crosslinking agent The photosensitive resin composition of this invention may contain a crosslinking agent 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 (excluding the component (A)). For example, adding a compound having two or more epoxy groups or oxetanyl groups in the molecule, an alkoxymethyl group-containing crosslinking agent, a compound having at least one ethylenically unsaturated double bond, a blocked isocyanate compound, etc. Can do.

  It is preferable that the addition amount of the crosslinking agent in the photosensitive resin composition of this invention is 0.01-50 mass parts with respect to a total of 100 mass parts of said (A) polymer, 0.1-30 mass parts. Part is more preferable, and 0.5 to 20 parts by mass is even more preferable. By adding in this range, a cured film excellent in 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.

<Compound having 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. For example, JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.) and the like, commercially available products described in paragraph number 0189 of JP2011-221494A, and the like can be mentioned.
As specific examples of the compound having two or more oxetanyl groups in the molecule, Aron oxetane OXT-121, OXT-221, OX-SQ, PNOX (manufactured by Toagosei Co., Ltd.) can be used.
Moreover, it is preferable to use the compound containing an oxetanyl group individually or in mixture with the compound containing an epoxy group.

<Block isocyanate compound>
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.
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, imide compounds, and the like. 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.

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-846N, 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, E402 -B80T (above, manufactured by Asahi Kasei Chemicals Corporation) Death Module BL1100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumidur BL3175 (above, Sumika Bayer Urethane Co., Ltd.), Karenz MOI-BP, Karenz MOI-BM (manufactured by Showa Denko KK) and the like can be preferably used.
As another crosslinking agent, for example, a methylated melamine resin (for example, Nicalac MW-30HM (manufactured by Sanwa Chemical Co., Ltd.)) can be used.

Antioxidant The photosensitive resin composition of the present invention may contain an antioxidant. As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives. Of these, phenol-based antioxidants, amide-based antioxidants, hydrazide-based antioxidants, and sulfur-based antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing film thickness, with phenol-based antioxidants being the most preferred. preferable. These may be used individually by 1 type and may mix 2 or more types.
Specific examples include compounds described in paragraph numbers 0026 to 0031 of JP-A-2005-29515, and compounds described in paragraph numbers 0106 to 0116 of JP-A-2001-227106. It is incorporated herein.
Preferred commercially available products include ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-330, IRGANOX 1726, and IRGA Knox 1035 and Irganox 1098 can be mentioned.

  The content of the antioxidant is preferably 0.1 to 10% by mass, more preferably 0.2 to 7% by mass, based on 100 parts by mass of the total amount of the polymer (A). It is particularly preferably 5 to 5% 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.

<Method for preparing photosensitive resin composition>
The composition of the present invention can be prepared by mixing each component at a predetermined ratio and by any method, and stirring and dissolving. For example, the resin composition can be prepared by mixing each component in a predetermined ratio after preparing each solution in advance in the above-described solvent. The composition solution prepared as described above can be used after being filtered using, for example, a filter having a pore diameter of 0.2 μm.

<Method for producing cured film>
Next, the manufacturing method of the cured film of this invention is demonstrated.
The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
(1) The process of applying the photosensitive resin composition of this invention on a board | substrate;
(2) removing the solvent from the applied photosensitive resin composition;
(3) The process of exposing the photosensitive resin composition from which the solvent was removed with actinic rays;
(4) A step of developing the exposed photosensitive resin composition with an aqueous developer;
(5) A developed post-baking step for thermosetting.
Each step will be described below in order.

In the application step (1), it is preferable to apply (preferably apply) the photosensitive resin composition of the present invention onto a substrate to form a wet film containing a solvent. It is preferable to perform substrate cleaning such as alkali cleaning or plasma cleaning before applying the photosensitive resin resin composition to the substrate, 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 inorganic substrates, resins, and resin composite materials.
Examples of the inorganic substrate include glass, quartz, silicone, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
The resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic Made of synthetic resin such as aromatic ether, maleimide-olefin, cellulose, episulfide compound And the like.
These substrates are rarely used in the above-described form, and usually a multilayer laminated structure such as a TFT element is formed depending on the form of the final product.
The application method to the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, or the like can be used.
The wet film thickness when applied is not particularly limited, and can be applied with a film thickness according to the application, but is usually used in the range of 0.5 to 10 μm.
Furthermore, before applying the composition used in the present invention to the substrate, it is possible to apply a so-called pre-wet method as described in JP-A-2009-145395.

  In the solvent removal step (2), the solvent is removed from the applied film by vacuum (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 an actinic ray having a predetermined pattern.
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, i-line (365 nm), h-line (405 nm), g-line ( Actinic rays having a wavelength of 300 nm to 450 nm, such as 436 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. The exposure amount is preferably 1 to 500 mj / cm ² .
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, a lens scanner, and a laser exposure can be used.

In the developing step (4), the copolymer having a carboxyl group or a phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing an exposed area containing a resin composition having a carboxyl group or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.
The developer used in the development step preferably contains a basic compound. Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
As a preferred developer, a 0.2 to 2.5% aqueous solution of tetramethylammonium hydroxide can be mentioned.
The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 500 seconds, and the development method may be any of a liquid piling method (paddle method), a shower method, a dipping method, and the like.
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, shower rinse and dip rinse can be mentioned.

In the post-baking step of (5), the cured film can be formed by crosslinking the acid group with a crosslinkable group, a crosslinking agent, etc. by heating the obtained positive image. This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 to 250 ° C. for a predetermined time, for example, 5 to 90 minutes on a hot plate, 30 to 120 minutes for an oven. It is preferable to By proceeding the crosslinking reaction in this way, a protective film and an interlayer insulating film that are superior in heat resistance, hardness, and the like can be formed. In addition, when the heat treatment is performed in a nitrogen atmosphere, the transparency can be further improved.
Prior to post-baking, post-baking can be performed after baking at a relatively low temperature (addition of a middle baking process). When performing middle baking, it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Moreover, middle baking and post-baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
Prior to post-baking, it is preferable from the viewpoint of improving transparency that the substrate on which the pattern is formed is re-exposed (post-exposure) with actinic rays. As a preferable exposure amount when a post-exposure step is included, 100 to 3,000 mJ / cm ² is preferable, and 100 to 2000 mJ / cm ² is particularly preferable.

  Furthermore, the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist. In the case where a cured film obtained by thermal curing in a post-baking process is used as a dry etching resist, dry etching processes such as ashing, plasma etching, and ozone etching can be performed as the etching process.

[Curing film]
The cured film of the present invention is a cured film obtained by curing the above-described photosensitive resin composition of the present invention.
The cured film of the present invention can be suitably used as an interlayer insulating film. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention mentioned above.
With the photosensitive resin composition of the present invention, an interlayer insulating film having excellent insulation and high transparency even when baked at high temperatures can be obtained. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film properties, it is useful for liquid crystal display devices and organic EL display devices.

[Liquid Crystal Display]
The liquid crystal display device of the present invention comprises the cured film of the present invention.
The liquid crystal display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and known liquid crystal displays having various structures. An apparatus 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 taken 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) disclosed in JP-A-2005-284291 or JP-A-2005-346054 is used. It can be used as an 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 microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.
FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix 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. Further, a flexible type can also be used, and it is used as the second interlayer insulating film (48) described in JP 2011-145686 A and the interlayer insulating film (520) described in JP 2009-258758 A. Can do.

[Organic EL display device]
The organic EL display device of the present invention comprises the cured film of the present invention.
The organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known structures having various structures. Examples thereof include an organic EL display device 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. 2 is a conceptual diagram of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
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 used to connect the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening layer 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 2, 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 second 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 is excellent in curability and cured film characteristics, a resist pattern formed using the photosensitive resin composition of the present invention as a structural member of a MEMS device can be used as a partition wall or mechanically driven. Used as part of the part. 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.

  Since the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. 2 of JP-A-2011-107476, JP-A-2010- The partition wall (12) and the planarization film (102) shown in FIG. 4A of 9793, and the bank layer (221) and the third interlayer insulating film (216b) shown in FIG. 10 of JP 2010-27591A. ), Second interlayer insulating film (125) and third interlayer insulating film (126) described in FIG. 4A of JP-A-2009-128577, and flatness described in FIG. 3 of JP-A-2010-182638. It can also be used to form a chemical film (12), a pixel isolation insulating film (14), and the like. In addition, spacers for maintaining the thickness of the liquid crystal layer in liquid crystal display devices, imaging optical systems for on-chip color filters such as facsimiles, electronic copying machines, solid-state image sensors, and micro lenses for optical fiber connectors are also used. It can be used suitably.

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 weight average molecular weight Mw of the copolymer was measured by gel permeation chromatography (GPC) under the following apparatus and conditions.
Apparatus: GPC-101 (made by Showa Denko KK)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined Mobile phase: Tetrahydrofuran Detector: Differential refractometer Standard material: Monodisperse polystyrene

<(A) Synthesis of polymer>
(Synthesis of P-1)
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 12 parts by weight of methacrylic acid, 50 parts by weight of glycidyl methacrylate, 4 parts by weight of N-cyclohexylmaleimide, 15 parts by weight of tetrahydrofurfuryl methacrylate, 5 parts by weight of acryloylmorpholine, 8 parts by weight of 3- (2-methacryloyloxyethyl) oxetane. And 2 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate) were charged and purged with nitrogen, followed by gentle stirring. The temperature of the solution was raised to 70 ° C., and the polymerization was started when the reaction solution temperature reached 70 ° C. Thereafter, 3 parts by mass of N-cyclohexylmaleimide 30 minutes after the start of polymerization, and 3 parts by mass of N-cyclohexylmaleimide were added dropwise to the reaction solution 1 hour later. Then, the polymer solution containing a copolymer (P-1) was obtained by hold | maintaining for 3 hours. The polystyrene equivalent weight average molecular weight (Mw) of the copolymer P-1 was 9,000, and the molecular weight distribution (Mw / Mn) was 2.0.

Other polymers were synthesized in the same manner as P-1 using the monomers listed in the following table (monomer components (raw materials of (a1) to (a3))), a polymerization initiator, a molecular weight regulator, and a solvent. did.
The numerical values in the following table that are not marked with a unit are in parts by mass.

<Preparation of photosensitive resin composition>
(A) component, (B) component, (C) component, alkoxysilane compound, and surfactant so that it may become the solid content ratio of the following table | surface, a solvent (Diethylene glycol ethyl methyl ether: Highsolve EDM (Toho Chemical Industry Co., Ltd.) To a solid content concentration of 32% by mass, and filtered through a polytetrafluoroethylene filter having a diameter of 0.2 μm to obtain photosensitive resin compositions of various Examples and Comparative Examples.

  The details of the abbreviations indicating the respective compounds used in Examples and Comparative Examples are as follows.

<(A) Polymer>
P-1 to P11: Polymers P-1 to P11 described in the above table
P-12: Cresol novolak type resin described in Example 1 of JP-A-11-223937

<(B) Quinonediazide compound>
B-1: 4,4 ′-[1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensate with sulfonic acid chloride (3.0 mol) B-2: 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid Condensate with chloride (2.0 mol) B-3: 2,3,4,4′-tetrahydroxybenzophenone (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid ester (2.44) Mole)

<(C) Nitrogen heterocyclic compound>
The following compounds (C-1) to (C-16) were used as nitrogen heterocyclic compounds.

(Alkoxysilane compound)
G-1: 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

(Surfactant)
W-1: Silicone surfactant ("SH 8400 FLUID" manufactured by Toray Dow Corning Co., Ltd.)
W-2: Fluorosurfactant FTX-218 (manufactured by Neos Co., Ltd.)

  The following evaluation was performed about the obtained composition.

<Evaluation of stripping solution resistance>
A glass substrate is exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and each photosensitive resin composition is spin-coated on the substrate, and then pre-baked on a hot plate at 90 ° C. for 120 seconds to volatilize the solvent. A photosensitive resin composition layer having a thickness of 3.0 μm was formed. Subsequently, exposure was performed using an ultrahigh pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm ² (illuminance: 20 mW / cm ² , i-line), and the substrate was heated in an oven at 230 ° C./30 minutes.
The film thickness (T1) of the obtained cured film was measured. And after immersing the board | substrate with which this cured film was formed in monoethanolamine temperature-controlled at 80 degreeC at 60 degreeC for 5 minutes, the film thickness (t1) of the cured film after immersion was measured, and the film | membrane by immersion Thickness change rate {| t1-T1 | / T1} × 100 [%] was calculated. The results are shown in the table below. A smaller value is preferable, and A and B are at a level causing no problem in practical use.
A: Less than 2% B: 2% or more and less than 3% C: 3% or more and less than 4% D: 4% or more and less than 6% E: 6% or more

<Evaluation of NMP resistance>
A glass substrate is exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and each photosensitive resin composition is spin-coated on the substrate, and then pre-baked on a hot plate at 90 ° C. for 120 seconds to volatilize the solvent. A photosensitive resin composition layer having a thickness of 3.0 μm was formed. Subsequently, using an ultra-high pressure mercury lamp, exposure was performed so that the integrated irradiation amount was 300 mJ / cm ² (illuminance: 20 mW / cm ² , i-line), and this substrate was heated in an oven at 230 ° C./30 minutes, Heated in an oven at 230 ° C./2 hours.
The film thickness (T1) of the obtained cured film was measured. And after immersing the board | substrate with which this cured film was formed in NMP (N-methylpyrrolidone) temperature-controlled at 80 degreeC for 10 minutes at 80 degreeC, the film thickness (t1) of the cured film after immersion was measured. Then, the film thickness change rate {| t1−T1 | / T1} × 100 [%] by immersion was calculated. The results are shown in the table below. A smaller value is preferable, and A and B are at a level causing no problem in practical use.
A: Less than 2% B: 2% or more and less than 3% C: 3% or more and less than 4% D: 4% or more and less than 6% E: 6% or more

<Evaluation of display unevenness (panel display unevenness) in display device>
A liquid crystal display device using a thin film transistor (TFT) was manufactured by the following method (see FIGS. 1 and 2). In the active matrix type liquid crystal display device described in FIG. 1 and FIG. 2 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows to obtain a liquid crystal display device.
That is, the bottom gate type TFT 1 was formed on the glass substrate 6, and the insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, after forming a contact hole in the insulating film 3, a wiring 2 (height of 1.0 μm) connected to the TFT 1 through the contact hole was formed on the insulating film 3.

Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarizing film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin compositions of Examples and Comparative Examples on a substrate, pre-baking (90 ° C. × 120 seconds) on a hot plate, After irradiating 25 mJ / cm ² (energy intensity 20 mW / cm ² ) with i-line (365 nm) using a high-pressure mercury lamp from above, a pattern is formed by developing with an alkaline aqueous solution, followed by heat treatment at 230 ° C. for 30 minutes. went.

A drive voltage is applied to the obtained liquid crystal display device, a gray test signal is input, the panel is continuously lit in an environment of 23 ° C., 50%, 1 atm, and the gray display after 1000 hours of lighting is visually observed. Observation was performed and the presence or absence of display unevenness was evaluated according to the following evaluation criteria.
A: No unevenness at all (very good)
B: Slight unevenness is observed on the edge of the glass substrate, but there is no problem in the display (good)
C: Slight unevenness on the display, but practical level (normal)
D: Display is uneven (somewhat bad)
E: Strong unevenness in display (very bad)

<Evaluation of panel display unevenness under severe conditions such as high temperature, high humidity, and high pressure (evaluation of panel reliability of display device)>
A liquid crystal display device was produced in the same manner as described above in <Evaluation of display unevenness (panel display unevenness) in the display device>. A drive voltage is applied to the obtained liquid crystal display device, a gray test signal is input, the panel is continuously lit in an environment of 60 ° C., 90%, 2 atm, and the gray display after 1000 hours of lighting is visually observed. Observation was performed and the presence or absence of display unevenness was evaluated according to the following evaluation criteria.
A: No unevenness at all (very good)
B: Slight unevenness is observed on the edge of the glass substrate, but there is no problem in the display (good)
C: Slight unevenness on the display, but practical level (normal)
D: Display is uneven (somewhat bad)
E: Strong unevenness in display (very bad)

  As is clear from the above results, the composition of the present invention comprises (A) (a1) a structural unit having an acid group, (a2) a polymer containing a structural unit having a crosslinkable group, (B) a quinonediazide compound, and (C) Since it contains at least one nitrogen-containing heterocyclic compound, it has excellent chemical resistance in the state of being a cured film, and is a panel of a display device when incorporated in a liquid crystal display device or the like as a cured film It was found that display unevenness can be further suppressed and panel display unevenness can be suppressed even when exposed to severe conditions such as high temperature, high humidity, and high pressure.

<Create organic EL display device>
An organic EL display device using a TFT was manufactured by the following method (see, for example, FIG. 1 of JP 2011-209681 A).
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 to the organic EL element formed between the TFTs 1 or in a later process.

Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening layer 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarizing film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 8 on a substrate, pre-baking on a hot plate (90 ° C. × 2 minutes), and then applying high pressure from above the mask. After irradiating i-line with 100 mJ / cm ² using a mercury lamp, a pattern was formed by developing with an alkaline aqueous solution, and heat treatment was performed at 220 ° C. for 60 minutes.

  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, a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped using a resist stripping solution (mixed solution of monoethanolamine and DMSO). The first electrode thus obtained corresponds to the anode of the organic EL element.

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

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

  As described above, an active matrix type organic EL display device in which each organic EL element is connected to the 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.

  1: TFT (thin film transistor), 2: wiring, 3: insulating film, 4: flattening film, 5: first electrode, 6: glass substrate, 7: contact hole, 8: insulating film, 10: liquid crystal display device, 12 : Backlight unit, 14, 15: Glass substrate, 16: TFT, 17: Cured film, 18: Contact hole, 19: ITO transparent electrode, 20: Liquid crystal, 22: Color filter

Claims (15)

(A) (a1) a polymer having a structural unit having an acid group and (a2) a structural unit having a crosslinkable group,
(B) a quinonediazide compound,
(C) at least one nitrogen-containing heterocyclic compound, and (D) a solvent,
The nitrogen-containing heterocyclic compound contains two or more nitrogen-containing aromatic rings, of which two nitrogen-containing aromatic rings are condensed or directly connected, and the nitrogen-containing aromatic ring is condensed or directly connected. The photosensitive resin composition which contains the structure of following formula (c-1) or the structure of following formula (c-2) in the structure which is.
(In the formula (c-1) or the formula (c-2), * represents a bonding site with another atom.) The photosensitivity according to claim 1, wherein the (C) at least one nitrogen-containing heterocyclic compound is at least one selected from nitrogen-containing heterocyclic compounds represented by the following general formulas (1) to (3). Resin composition.
(In the general formula (1), R ¹ and R ² each represent a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an amino group, a halogen atom, or a mercapto group. It represents an integer of 2. In general formula (2), R ^{3 to} R ⁵ each represent a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an amino group, a halogen atom, or a mercapto group, and q is R represents an integer of 0 to 2, and r and s each represent an integer of 0 to 3. In the general formula (3), R ⁶ and R ⁷ are a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, an alkyl group, respectively. A group, an amino group, a halogen atom or a mercapto group, and t and u each represents an integer of 0 to 4) The (C) at least one nitrogen-containing heterocyclic compound is at least selected from nitrogen-containing heterocyclic compounds represented by the following general formula (1-1), the general formula (2), or the general formula (3). The photosensitive resin composition of Claim 2 which is 1 type.
(In the general formula (1-1), R ¹¹ and R ²¹ each represent a hydrogen atom, a hydroxyl group, a sulfonic acid group, and an alkyl group. X ¹ represents a hydrogen atom, an acyl group, and an alkyl group. P1 is 0. Represents an integer of ~ 2) The nitrogen heterocyclic compound is 4-hydroxypteridine, 2-ethyl-4-hydroxypteridine, 1,10-phenanthroline, 5-methyl-1,10-phenanthroline, 2,2′-bipyridine and 5,5′-dimethyl. The photosensitive resin composition of any one of Claims 1-3 which is at least 1 sort (s) of -2,2'-bipyridine. The photosensitive resin composition of any one of Claims 1-4 whose said structural unit (a1) is a structural unit which has a carboxyl group and / or a phenolic hydroxyl group. The structural unit (a2) is at least selected from the group consisting of an epoxy group, an oxetanyl group and a group represented by —NH—CH ₂ —O—R (where R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). The photosensitive resin composition of any one of Claims 1-5 containing the structural unit containing one. The photosensitive resin composition of any one of Claims 1-6 whose compounding quantity of the said (B) quinonediazide compound is 10-50 mass parts with respect to a total of 100 mass parts of the said (A) polymer component. object. The photosensitive resin composition of any one of Claims 1-7 in which the said (A) polymer contains the structural unit derived from (meth) acrylic acid. The photosensitive resin composition of any one of Claims 1-8 which is a positive type. (1) The process of apply | coating the photosensitive resin composition of any one of Claims 1-9 on a board | substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays,
(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) a post-baking step of thermosetting the developed photosensitive resin composition;
The manufacturing method of the cured film containing this. The manufacturing method of the cured film of Claim 10 including the process of exposing the developed photosensitive resin composition to the whole surface after the said image development process and before the said post-baking process. The manufacturing method of the cured film of Claim 10 or 11 including the process of dry-etching with respect to the board | substrate which has a cured film obtained by thermosetting at the said post-baking process. It formed with the manufacturing method of the cured film formed by hardening | curing the photosensitive resin composition of any one of Claims 1-9, or the cured film of any one of Claims 10-12. Cured film. The cured film of Claim 13 which is an interlayer insulation film. An organic EL display device or a liquid crystal display device having the cured film according to claim 13 or 14.