JP5477527B2 - Positive photosensitive resin composition containing terminal functional group-containing polyimide - Google Patents

Description

  The present invention relates to a photosensitive material suitable for a surface protective film, an interlayer insulating film, a passivation film, an electrode protective layer, etc. for electrical / electronic devices, particularly semiconductor devices and display devices. More specifically, an excellent positive photosensitive resin composition that is soluble in a low-pollution organic solvent and that does not cause poor light emission on the light emitting surface when the obtained cured film is used as an insulating film of an organic EL device. And a cured film thereof, and various materials using the cured film.

  Photosensitive insulating films made from photosensitive resins represented by photosensitive polyimide resins with excellent mechanical properties and high heat resistance have expanded their use, and have begun to spread not only in the semiconductor field but also in the display field. . In particular, when the photosensitive insulating film is used for a display device such as a protective film of a thin film transistor (TFT) of a liquid crystal display element and an electrode protective film of an organic EL element, the above-mentioned performance is of course further insulated. The reliability of the film is required, and from the viewpoint of simplification of the device manufacturing process, good shape of the protective film, and productivity, it is a low pollution system and is soluble in biodegradable solvents. Some characteristics are also required. In particular, in the above-described apparatus, since it is an important condition not to cause a display defect, it is required not to cause an element defect due to moisture or oozing out of a photosensitive agent from a cured film incorporated in a final product. .

The positive type photosensitive resin compositions that have been proposed so far use a basic organic compound such as triethylamine to reduce the acidity of the polyamic acid and suppress the dissolution rate in an alkaline developer. Type photosensitive resin composition (Patent Document 1). Also, a positive photosensitive resin composition comprising a polyimide resin containing a phenolic hydroxy group and a non-phenolic hydroxy group and a quinonediazide compound for the purpose of improving the remaining film retention rate and mechanical strength after thermosetting (patented) Document 2), a resin composition in which a phenolic compound is added in addition to polyamide and diazoquinone compound, which are polyimide precursors, for the purpose of improving sensitivity, high residual film ratio, and adhesion with a sealing resin. It has been proposed (Patent Document 3).
U.S. Pat. No. 4,880,722 Japanese Patent No. 2004-94118 JP-A-9-302221

Although the materials proposed in the above-mentioned patent documents are described as having high sensitivity and excellent mechanical properties, the material light emitting surface due to exudation of additives (such as triethylamine and phenolic compounds) from the final cured film. Was a concern.
As described above, in the conventional positive photosensitive composition using a polyimide resin, it is difficult to provide a material satisfying the light emission characteristics as a partition wall of the light emitting element, particularly when it is assumed to be used in a display element.

  The present invention has been made in view of the above circumstances, and provides a positive photosensitive resin composition that is a display element material that enables a clear image to be displayed in a display device such as an organic EL device. It is. Furthermore, the present invention intends to provide a positive photosensitive resin composition that is soluble in a low pollution organic solvent.

As a result of intensive studies in order to achieve the above object, the present inventor can form a fine pattern by using a positive photosensitive resin composition containing a polyimide compound having a terminal functional group, and an organic EL device Was found to display a clear light-emitting surface, and the present invention was completed.
That is, as a first aspect, the component (A) contains a polyimide represented by the following formula (1), and the component (B) contains a compound that generates an acid by light. The present invention relates to a dissolved positive photosensitive resin composition.

(In the formula, X represents a tetravalent aliphatic group or an aromatic group,
Y represents a divalent organic group containing an aromatic group substituted with at least one OH group;
Z ¹ and Z ² each represents an organic group containing an alkali-solubilizing group that makes the polyimide soluble in an alkaline solution independently of each other;
Q ¹ represents a hydrogen atom, or together with the adjacent Z ¹ forms a ring structure,
Q ² represents a hydrogen atom or together with adjacent Z ² forms a ring structure,
m represents an integer of 1 or more. )
As a second aspect, the present invention relates to the positive photosensitive resin composition according to the ^{first aspect} , wherein at least one of Z ¹ and Z ² is an organic group containing an alkali solubilizing group and an aromatic group.
As a third aspect, Z ¹ and Z ² are a group represented by the following formula (2) or (3), or Z ¹ and Q ¹ or Z ² and Q ² together are represented by the following formula: The positive photosensitive resin composition according to the first aspect or the second aspect, which forms the group represented by (4).

As a fourth aspect, the positive photosensitive film according to any one of the first to third aspects, wherein Y is a divalent organic group containing a benzene ring substituted with at least one OH group. The present invention relates to a functional resin composition.
As a fifth aspect, according to any one of the first to fourth aspects, the Y is a divalent organic group containing two or more benzene rings substituted with at least one OH group. The present invention relates to a positive photosensitive resin composition.
As a sixth aspect, any one of the first aspect to the fifth aspect, wherein the Y includes at least one structure selected from the group consisting of structures represented by the following formulas (5) to (7): The positive photosensitive resin composition according to one item.

Wherein R ^{1 to} R ²⁷ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, Atom, nitro group, formyl group, cyano group, carboxyl group, phospho group, sulfo group, phenyl group optionally substituted with W, naphthyl group optionally substituted with W, optionally substituted with W Represents a thienyl group or a furyl group optionally substituted by W;
W is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, or a carboxyl group. Represents a phospho group or a sulfo group,
Z ^{1 to} Z ⁶ are a single bond, an alkylene group having 1 to 10 carbon atoms which may be substituted with W ¹ , —C (O) O—, —C (O) NH—, —O—, — S-, -S (O) ₂ -or -C (
O)-
W ¹ represents an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, p to x represent an integer of 1 or more, and 2 ≧ p + q ≧ 1, 3 ≧ r + s + t ≧ 1, 4 ≧ u + v + w + x ≧ 1. )
As a seventh aspect, the Z ^{3 to} Z ⁷ are each a single bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —C (
CF ₃ ) ₂ —, —C (O) NH—, —O—, —S (O) ₂ — or —C (O) —
It is related with the positive photosensitive resin composition as described in any one of a viewpoint thru | or a 6th viewpoint.
As an eighth aspect, the positive type according to any one of the first to seventh aspects, wherein the component (A) is a polyimide further including at least one structure represented by the following formula (9): The present invention relates to a photosensitive resin composition.

(Where
R ^{29 to} R ³² are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, or a nitro group. , formyl group, a cyano group, a carboxyl group, a phospho group, a sulfo group, a phenyl group which may be substituted with W ^2, a naphthyl group which may be substituted with W ^2, which may be substituted with W ^2-thienyl Represents a furyl group optionally substituted by a group or W ² ,
W ² is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms,
Represents an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group, a phospho group or a sulfo group;
Z ^{7 to} Z ⁹ are each independently a single bond, an alkylene group having 1 to 10 carbon atoms which may be substituted with W ³ , —C (O) O—, —C (O) NH—, -O-, -S-, -S (O) _2- or -C (O)-
W ³ represents an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and
q represents an integer of 1 or more. )
As a ninth aspect, in the above formula (9), R ^{29 to} R ³² represent a methyl group, Z ⁷ represents —O—, and Z ^{8 to} Z ⁹ represent a propylene group. Type photosensitive resin composition.
As a tenth aspect, the component (A) is a polyimide obtained from a polyimide precursor obtained by polymerizing a tetracarboxylic acid component containing a compound represented by the following formula (8) and a diamine component, It is related with the positive photosensitive resin composition as described in any one of a viewpoint thru | or a 9th viewpoint.

(In the formula, R ²⁸ represents a divalent group having a sulfur atom.)
As an eleventh aspect, the present invention relates to the positive photosensitive resin composition according to the tenth aspect, in which the compound represented by the formula (8) accounts for 40 to 99 mol% in the tetracarboxylic acid component.
As a twelfth aspect, the present invention relates to the positive photosensitive resin composition according to the tenth aspect or the eleventh aspect, wherein R ²⁸ in formula (8) is a divalent group having a sulfonyl group.
As a thirteenth aspect, the present invention relates to the positive photosensitive resin composition according to any one of the first to twelfth aspects, wherein the component (B) is a naphthoquinone diazide sulfonic acid ester compound.
As a fourteenth aspect, in any one of the first to thirteenth aspects, (C) the solvent is at least one selected from the group consisting of an alcohol having 4 or more carbon atoms or an alkyl ester. It relates to the positive photosensitive resin composition described.
As a fifteenth aspect, the positive electrode according to any one of the first to fourteenth aspects, containing 0.01 to 100 parts by mass of the component (B) based on 100 parts by mass of the component (A). Type photosensitive resin composition.
As a sixteenth aspect, the maleimide compound represented by the following (10) as the component (D) further contains 5 to 100 parts by mass based on 100 parts by mass of the component (A), and the positive type according to the fifteenth aspect The present invention relates to a photosensitive resin composition.

(In the formula, R ³³ represents a divalent group, and R ^{34 to} R ⁴³ each independently represents a hydrogen atom or an organic group having 1 to 12 carbon atoms.)
As a seventeenth aspect, the present invention relates to the positive photosensitive resin composition according to the sixteenth aspect, wherein R ³³ has a structure represented by the following formula (11) in the formula (10).

(Wherein l and k each independently represent 0 or 1, R ^{44 to} R ⁴⁶ each independently represent a divalent organic group having 1 to 12 carbon atoms, an oxygen atom, a sulfur atom, or Represents a divalent group having a nitrogen atom.)
As an eighteenth aspect, in the formula (11), l and k represent 1, R ⁴⁴ and R ⁴⁶ represent an oxygen atom, and R ⁴⁵ represents a dimethylmethylene group. The present invention relates to a resin composition.
As a nineteenth aspect, the isocyanuric compound represented by the following formula (12) as the component (E) further contains 3 to 100 parts by mass based on 100 parts by mass of the component (A), the fifteenth aspect to the eighteenth aspect. It relates to the positive photosensitive resin composition as described in any one of these.

(Wherein R ^{47 to} R ⁴⁹ each independently represents an organic group having a structure of an epoxy group, an oxetane group, a urethane group, an allyl group, or an acrylic group.)
As a twentieth aspect, in the above formula (12), R ^{46 to} R ⁴⁸ are any groups represented by the following formulas (13) to (15), and the positive photosensitive resin according to the nineteenth aspect Relates to the composition.

(Wherein R ^{50 to} R ⁵⁸ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom) atom, a nitro group, a formyl group, a cyano group, a carboxyl group, a phospho group, a sulfo group, W optionally substituted phenyl group ^4, W ⁴ optionally substituted by a naphthyl group, W ⁴
Represents a thienyl group optionally substituted with or a furyl group optionally substituted with W ⁴ ;
W ⁴ is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms,
An alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group, a phospho group, or a sulfo group is represented. )
As a 21st viewpoint, it is related with the cured film obtained using the positive photosensitive resin composition as described in any one of a 1st viewpoint thru | or a 20th viewpoint.
As a 22nd viewpoint, it is related with the electronic component which has a cured film as described in a 21st viewpoint.
As a 23rd viewpoint, it is related with the organic EL element which has the cured film as described in a 21st viewpoint.
As a twenty-fourth aspect, the positive photosensitive resin composition according to any one of the first to twentieth aspects is applied onto a substrate, heated and dried, and then developed by irradiation with ultraviolet rays. The present invention relates to a pattern forming method.
As a 25th viewpoint, the following formula (1)

(In the formula, X represents a tetravalent aliphatic group or an aromatic group,
Y represents a divalent organic group containing an aromatic group substituted with at least one OH group;
Z ¹ and Z ² are groups represented by the following formula (2) or (3), or Z ¹ and Q ¹ or Z ² and Q ² together are represented by the following formula (4). Forming a group,

（式中、Ｘは、４価の脂肪族基又は芳香族基を表し、
Ｙは、少なくとも１つのＯＨ基で置換された芳香族基を含む２価の有機基を表し、
Ｚ ^１ 及びＺ ^２ は、下記式（２）で表される基を表すか、又は、Ｚ ^１ とＱ ^１ 若しくはＺ ^２ とＱ ^２ が一緒になって下記式（４）で表される基を形成し、

Ｑ ^１ は水素原子を表すか、又は、隣接するＺ ^１ と一緒になって環構造を形成し、
Ｑ ^２ は水素原子を表すか、又は、隣接するＺ ^１ と一緒になって環構造を形成し、
ｍは１以上の整数を表す。）
Q ¹ represents a hydrogen atom, or together with adjacent Z ¹ forms a ring structure,
Q ² represents a hydrogen atom or together with adjacent Z ² forms a ring structure,
m represents an integer of 1 or more. )
It is related with the polyimide represented by these.
Especially this invention contains the compound represented by following formula (1) as (A) component, and the compound which generate | occur | produces an acid by light as (B) component, and these melt | dissolved in (C) solvent. It is intended for positive-type photosensitive resin compositions and polyimides represented by the following formula (1).

(In the formula, X represents a tetravalent aliphatic group or an aromatic group,
Y represents a divalent organic group containing an aromatic group substituted with at least one OH group;
Z ¹ and Z ² represent a group represented by the following formula (2), or a group represented by the following formula (4) by combining Z ¹ and Q ¹ or Z ² and Q ² together. Forming,

Q ¹ represents a hydrogen atom, or together with adjacent Z ¹ forms a ring structure,
Q ² represents a hydrogen atom, or together with the adjacent Z ¹ forms a ring structure,
m represents an integer of 1 or more. )

  The positive photosensitive resin composition of the present invention is uniformly dissolved in a low-pollution organic solvent, for example, a solvent such as propylene glycol monomethyl ether acetate (PGMEA) used in a photoresist material, and causes a problem during development. A thin pattern with excellent resolution can be formed without film loss in unexposed areas. In addition, the organic EL element using a film cured after pattern formation displays an effect of displaying a clear light emitting surface without a shadow.

[Positive photosensitive resin composition]
The positive-type photosensitive resin composition of the present invention contains (A) component polyimide and (B) component photoacid generator, which are dissolved in (C) solvent, and, if desired, It is a composition containing other additives such as a maleimide compound as component (D), an isocyanuric compound as component (E), and a surfactant.

<(A) component>
The component (A) is a polyimide represented by the following formula (1).

In said formula, m represents the polymerization degree of the polyimide represented by Formula (1). m is a positive integer of 1 or more, but when n is larger than 1000, the solubility in a general organic solvent is extremely lowered, the viscosity of the resin composition solution is remarkably increased, and the handling property is deteriorated. There is. For this reason, in consideration of solubility, m is preferably a positive integer of 1 or more and 1000 or less, and more preferably a positive integer of less than 100.

  In the above formula (1), X represents a tetravalent aliphatic group or an aromatic group, and these structures are not particularly limited as long as they are a tetravalent aliphatic group or an aromatic group. Moreover, in the polyimide represented by Formula (1), the structure of the organic group represented by X may be one type, or a plurality of types may be mixed.

  Preferably, the organic group represented by X includes a group represented by the following formula (16).

In the formula, R ²⁸ represents a divalent group having a sulfur atom, and is not particularly limited, but is preferably a sulfonyl group, a sulfide group, or a sulfoxide group from the viewpoint of the solubility of the resulting polymer and the reliability of the device. In particular, a sulfonyl group is more preferable.

In the above formula (1), Y represents a divalent organic group containing an aromatic group substituted with at least one OH group, preferably containing a benzene ring substituted with at least one OH group, more preferably A divalent organic group containing two or more benzene rings is desirable.
Specifically, Y is preferably a structure represented by the following formulas (5) to (7).

In the above formulas (5) to (7), R ^{1 to} R ²⁷ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or the number of carbon atoms. 1 to 10 alkoxy groups, halogen atom, nitro group, formyl group, cyano group, carboxyl group, phospho group, sulfo group, phenyl group optionally substituted with W, naphthyl group optionally substituted with W, It represents a thienyl group optionally substituted with W or a furyl group optionally substituted with W.
W is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, or a carboxyl group. Represents a phospho group or a sulfo group.
Z ^{1 to} Z ⁶ are a single bond, an alkylene group having 1 to 10 carbon atoms which may be substituted with W ¹ , —C (O) O—, —C (O) NH—, —O—, — S-, -S (O) ₂ -or -C (
O)-.
W ¹ represents an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
P to x represent an integer of 1 or more, and satisfy 2 ≧ p + q ≧ 1, 3 ≧ r + s + t ≧ 1, 4 ≧ u + v + w + x ≧ 1.

In the above formulas (5) to (7), Z ^{3 to} Z ⁷ are a single bond, —CH ₂ —, —C (CH ₃ ) ₂ —.
, —C (CF ₃ ) ₂ —, —C (O) NH—, —O—, —S (O) ₂ — or —C (O) — is desirable.

In the above formula (1), Z ¹ and Z ² each independently represent an organic group containing an alkali solubilizing group that makes the polyimide soluble in an alkaline solution, more preferably at least ^one of Z ¹ and Z ² It is desirable that one is an organic group containing an aromatic group in addition to an alkali solubilizing group. The alkaline solution referred to here typically indicates an alkaline developer described later. After exposing the coating film obtained from the positive photosensitive resin composition of the present invention, when removing the unexposed portion with an alkaline developer, the alkali solubilizing group promotes dissolution in the developer, and The dissolution rate in the developer can be adjusted by appropriately selecting the alkali-solubilizing group.
Examples of the alkali solubilizing group include a carboxyl group, a (phenolic) hydroxy group, a sulfonic acid group, and a thiol group, and among them, a carboxyl group is preferable.

In formula (1), Q ¹ and Q ² each represent a hydrogen atom, or are formed together with adjacent Z ¹ or Z ² to form a ring structure.

In particular, Z ¹ and Z ² are groups represented by the following formula (2) or (3), or Z ¹ and Q ¹ or Z ² and Q ² are combined to form the following formula (4 It is desirable to form a group represented by

In the above formula (1), Z ¹ and Z ² are groups represented by the above formula (2) or (3), or Z ¹ and Q ¹ or Z ² and Q ² are together. The polyimide which forms the group represented by the above formula (4) is also one aspect of the present invention.

  In addition, the polyimide represented by the formula (1) of the component (A) may further include at least one structure represented by the following formula (9).

In the above formula, R ^{29 to} R ³² each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, atom, a nitro group, a formyl group, a cyano group, a carboxyl group, a phospho group, a sulfo group, an optionally substituted phenyl group W ^2, W ² in which may be substituted naphthyl group, substituted with W ² It represents a thienyl group which may be substituted or a furyl group which may be substituted with W ² .
W ² is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group Represents a group, a phospho group or a sulfo group.
Z ^{7 to} Z ⁹ each independently represents a single bond or a carbon atom which may be substituted with W ^3.
To 10 alkylene groups, —C (O) O—, —C (O) NH—, —O—, —S—, —S (O) ₂ — or —C (O) —.
W ³ represents an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
Q represents an integer of 1 or more.

In the above formula (9), it is particularly preferable that R ^{29 to} R ³² represent a methyl group, Z ⁷ represents —O—, and Z ^{8 to} Z ⁹ represent a propylene group.

[Production method of polyimide]
The polyimide (A) component used in the positive photosensitive resin composition of the present invention is a polyimide precursor obtained by polymerizing tetracarboxylic dianhydride and its derivative (tetracarboxylic acid component) and diamine (diamine component). After obtaining (polyamic acid), it is a polyimide obtained by imidizing the precursor, and in the polyimide production process, the end of the polyimide (or polyimide precursor) is terminated at an appropriate stage. It is the polyimide sealed with.

<Tetracarboxylic dianhydride and its derivative>
Tetracarboxylic dianhydride and derivatives thereof are compounds represented by the following general formula (17), wherein X represents a tetravalent aliphatic group or an aromatic group, and these structures are tetravalent. If it is an aliphatic group or an aromatic group, it will not specifically limit.
Moreover, in manufacture of the polyimide used for this invention, tetracarboxylic dianhydride and its derivative (s) may use 1 type of compounds which have a structure represented by a following formula, or may use multiple types.

  Particularly preferred are tetracarboxylic dianhydrides represented by the following formula (8) and derivatives thereof.

In the formula, R ²⁸ represents a divalent group having a sulfur atom. Although it is not particularly limited as long as it is a divalent group having a sulfur atom, it is preferably a divalent group having a sulfonyl group, a sulfide group, or a sulfoxide group from the viewpoint of the solubility of the resulting polymer and the reliability of the device. In particular, a sulfonyl group is more preferable.

  Specific examples of the acid component having a sulfur atom include 3,3 ′, 4,4′-diphenyl sulfide tetracarboxylic acid component compound, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic acid component compound, 3,3 ′. , 4,4′-diphenylsulfoxide tetracarboxylic acid component compounds and the like, but are not limited to these compounds.

  Further, as the tetracarboxylic acid component, a compound other than the compound represented by the above formula (8) (compound having a sulfur atom), that is, a tetracarboxylic acid component not containing a sulfur atom may be included. In this case, it is preferable to use the tetracarboxylic acid component represented by the above formula (8): a tetracarboxylic acid component not containing a sulfur atom in a molar ratio range of 40:60 to 99: 1.

  Examples of the tetracarboxylic acid component not containing a sulfur atom include compounds represented by the following formulas (18) to (21). Two or more of these acid components may be used in the copolymerization. In particular, from the viewpoint of device reliability, the molar ratio of the acid component having a sulfur atom and the acid component not containing a sulfur atom is preferably 50:50 to 80:20.

In formula (18), R ⁵⁹ represents an organic group having 1 to 12 carbon atoms or a divalent organic group having an oxygen atom directly connected to an aromatic ring. R ⁵⁹ is not particularly limited as long as it is an organic group that satisfies the above conditions. Examples of the organic group having 1 to 12 carbon atoms include an alkyl group, a fluoroalkyl group, a cycloalkyl group, and an aromatic group, and an oxygen atom Examples of the divalent organic group having an ether group or a siloxy group. Among these, R ⁵⁹ is preferably a fluoroalkyl group or an ether group from the viewpoint of solubility and photosensitive characteristics, and particularly preferably a fluoromethyl group from the viewpoint of solubility.

  In formula (19), j represents an integer of 0 or 1.

In the formula (20), R ⁶⁰ and R ⁶¹ represent an organic group having 1 to 12 carbon atoms. R ⁶⁰ and R ⁶¹ may be any organic group as long as it is an organic group having 1 to 12 carbon atoms. Examples include, but are not limited to, alkyl groups, fluoroalkyl groups, cycloalkyl groups, or aromatic groups.

In the formula (21), R ⁶² represents a divalent organic group having 1 to 12 carbon atoms, and R ⁶³ and R ⁶⁴ represent an organic group having 1 to 12 carbon atoms. Examples of the divalent organic group having 1 to 12 carbon atoms of R ⁶² include a methylene group, an ether group, a trialkylsilyl group, and a dialkyldisiloxy group, but are not particularly limited to these organic groups. . R ⁶³ and R ⁶⁴ are not particularly limited as long as they are organic groups having 1 to 12 carbon atoms. Examples thereof include alkyl groups, fluoroalkyl groups, cycloalkyl groups, and aromatic groups.

Specific examples of the acid component not containing a sulfur atom represented by the above formulas (18) to (21) include 2,2-bis (3,4-dicarboxyphenyl) hexafluoroisopropylidene, 4,4′-hexa. Fluoroisopropylidene diphthalic acid, pyromellitic acid, 1,2,6,7-naphthalenetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 3,3 ′
, 4,4′-benzophenone tetracarboxylic acid, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid component A representative aromatic tetracarboxylic acid component, or 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3, 4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 5- (2, 5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid, 2,3,5-tricarboxy-2-cyclopentaneacetic acid, bicyclo [2. .2] Fats such as octo-7-ene-2,3,5,6-tetracarboxylic acid, 2,3,4,5-tetrahydrofurantetracarboxylic acid, 3,5,6-tricarboxy-2-norbornaneacetic acid Although a cyclic tetracarboxylic acid component can be mentioned, it is not limited to these.

  Among the acid components containing no sulfur atom, 2,2-bis (3,4-dicarboxyphenyl) hexafluoroisopropylidene and 4,4′-hexa are particularly preferred from the viewpoint of the solubility and photosensitivity of the resulting polymer. It is desirable to use fluoroisopropylidene diphthalic acid, pyromellitic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid and derivatives thereof, and in particular, 4,4′-hexa from the viewpoint of solubility of the resulting polymer. It is desirable to use compounds such as fluoroisopropylidene diphthalic dianhydride and its dihalide.

<Diamine>
Diamine is a compound having a structure represented by the following general formula (22), wherein Y represents a divalent organic group containing an aromatic group substituted with at least one OH group, preferably at least 1 It is a divalent organic group containing two or more benzene rings substituted with one OH group. These structures are not particularly limited as long as they are divalent organic groups including an aromatic group substituted with at least one OH group.
Moreover, in manufacture of the polyimide used for this invention, diamine may use 1 type of compounds which have a structure represented by a following formula, or may use multiple types.

Specific examples of the diamine having an aromatic group substituted with at least one OH group represented by the above formula (22) include 2,4-diaminophenol, 3,5-diaminophenol, and 2,5-diaminophenol. 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, 3,3′-dihydroxybenzidine (3BP), 3,3′-diamino-4,4′-dihydroxybiphenyl (4BP), 3,3′-diamino -2,2'-dihydroxybiphenyl (2BP), bis (3-amino-4-hydroxyphenyl) methane (BAPF), bis (4-amino-3-hydroxyphenyl) methane, bis (4-amino-3,5 −
Dihydroxyphenyl) methane, 2,2′-bis (3-amino-4-hydroxyphenyl) propane (BAPA), 2,2′-bis (4-amino-3-hydroxyphenyl) propane, 2,2′-bis (4-amino-3,5-dihydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF), 2,2-bis (4-amino-3-hydroxyphenyl) ) Hexafluoropropane, 2,2-bis (4-amino-3,5-dihydroxyphenyl) hexafluoropropane, 2,2-bis [4- (3-amino-4-hydroxyphenoxy) phenyl] hexafluoropropane, (3-amino-4-hydroxy) phenyl (3-amino-4-hydroxy) anilide (AHPA), bis (3-amino 4-hydroxyphenyl) ether (AHPE), bis (4-amino-3-hydroxyphenyl) ether, bis (4-amino-3,5-dihydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) sulfide (BSDA), bis (4-amino-3-hydroxyphenyl) sulfide, bis (4-amino-3,5-dihydroxyphenyl) sulfide, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino) -3-hydroxyphenyl) sulfone, bis (4-amino-3,5-dihydroxyphenyl) sulfone, 3,3'-diamino-4,4'-dihydroxybenzophenone (AHPK), 4,4'-diamino-3, 3'-dihydroxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-di Droxy-5,5′-dimethoxybiphenyl, 1,4-bis (3-amino-4-hydroxyphenoxy) benzene, 1,3-bis (3-amino-4-hydroxyphenoxy) benzene, 1,4-bis ( 4-amino-3-hydroxyphenoxy) benzene, 1,3-bis (4-amino-3-hydroxyphenoxy) benzene, bis [4- (3-amino-4-hydroxyphenoxy) phenyl] sulfone, bis [4- (3-Amino-4-hydroxyphenoxy) phenyl] propane, 2-amino-4- (3- (4-amino-3-hydroxyphenoxy) phenoxy) phenol, 5,5 ′-(1,3-phenylenebis ( Oxy)) bis (2-aminophenol), 5,5 ′-(1,4-phenylenebis (oxy)) bis (2-aminophenol), 2-a No-4- (4- (4-amino-3-hydroxyphenoxy) phenoxy) phenol, 2-amino-4- (3- (3- (4-amino-3-hydroxyphenoxy) phenoxy) phenoxy) phenol, 5 , 5 ′-(3,3′-oxybis (3,1-phenylene) bis (oxy)) bis (2-aminophenol), 4,4 ′-(4,1′-oxybis (4,1-phenylene) Bis (oxy)) bis (2-aminophenol), 2-amino-4- (4- (4- (4-amino-3-hydroxyphenoxy) phenoxy) phenoxy) phenol, and the like. There is nothing to do.

  Particularly preferred is a diamine represented by the following formulas (23) to (25).

In the above formulas (23) to (25), R ^{1 to} R ²⁷ , Z ^{1 to} Z ⁶ , and p to x are the above formulas (
5) to the same meaning as defined in formula (7).

As specific examples of the diamines represented by the above formulas (23) to (25), bis (3-amino-4-hydroxyphenyl) methane (BAPF), 2,2′-bis (3-amino) are preferable. -4-hydroxyphenyl) propane (BAPA), 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF), bis (3-amino-4-hydroxyphenyl) ether (AHPE), 3,3′-diamino-4,4′-dihydroxybenzophenone (AHPK), bis (3-amino-4-hydroxyphenyl) sulfide (BSDA), (3-amino-4-hydroxy) phenyl (3-amino-4) -Hydroxy) anilide (AHPA) and the like.
In particular, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) may be mentioned as a more suitable compound from the viewpoint of the solubility of the polymer obtained and the photosensitive properties.

In addition to the diamine containing an aromatic group substituted with at least one OH group as described above, other diamines can also be used.
Although it does not specifically limit as another diamine component, Preferably it is a diamine containing an aromatic group, especially a diamine containing one or more benzene rings.
When the other diamine component is used, the diamine component containing the aromatic group substituted with the at least one OH group: the other diamine component has a molar ratio of 70:30 to 99: 1, and is photosensitive. From the viewpoint of characteristics, it is more preferable to use in the range of 80:20 to 95: 5.

Examples of the other diamines include 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2- Bis (4-anilino) hexafluoropropane, 2,2-bis (3-anilino) hexafluoropropane or 2,2-bis (3-amino-4-toluyl) hexafluoropropane, p-phenylenediamine, m-phenylene Diamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfide, 4,4 ′ Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4-methylene - bis (2
-Methylaniline), 4,4'-methylene-bis (2,6-dimethylaniline), 4,4-methylene-bis (2,6-diethylaniline), 4,4'-methylene-bis (2-isopropyl) -6-methylaniline) 4,4'-methylene-bis (2,6-diisopropylaniline), 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, benzidine, o-tolidine, m-tolidine 3,3 ′, 5,5′-tetramethylbenzidine, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1,3-benzene Dicarboxylic acid, 2,5-diamino-1,4-benzenedicarboxylic acid, bis (4-amino-3-carboxyphenyl) ether, bis (4-amino-3,5-dicarboxypheny) ) Ether, bis (4-amino-3-carboxyphenyl) sulfone, bis (4-amino-3,5-dicarboxyphenyl) sulfone, 4,4′-diamino-3,3′-dicarboxybiphenyl, 4, 4′-diamino-3,3′-dicarboxy-5,5′-dimethylbiphenyl, 4,4′-diamino-3,3′-dicarboxy-5,5′-dimethoxybiphenyl, 1,4-bis ( 4-amino-3-carboxyphenoxy) benzene, 1,3-bis (4-amino-3-carboxyphenoxy) benzene, bis [4- (4-amino-3-carboxyphenoxy) phenyl] sulfone, bis [4- A compound such as (4-amino-3-carboxyphenoxy) phenyl] propane may be mentioned, but is not limited thereto. In addition, from the viewpoint of the solubility and photosensitivity of the obtained polymer, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, Is desirable.

Furthermore, as a diamine component which is a monomer component constituting the polyhydroxyamide resin (A) used in the present invention, in addition to the diamine containing an aromatic group substituted with at least one OH group, a siloxane-containing diamine Can also be used. By using the siloxane-containing diamine in combination, the adhesion of the coating film made of the polyhydroxyamide resin (A) to the substrate can be improved.
As such a siloxane-containing diamine, bis (3-aminoalkyl) -1,1,3,3-tetramethyldisiloxane is desirable, and bis (3-aminopropyl) is used from the viewpoint of adhesion to the substrate and solubility. -1,1,3,3-tetramethyldisiloxane (APDS) is more preferable.

《End sealant》
When the polyimide used in the present invention is converted into a polyimide from the tetracarboxylic acid component and the diamine component through a polyimide precursor, the end is sealed with a terminal sealing agent at an appropriate stage.
As the end-capping agent used here, a compound having an alkali-solubilizing group is easily introduced even after introduction into the N-terminus of the polyimide precursor or polyimide.

Examples thereof include acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, and the like. These compounds can be used singly or in combination of two or more. From the viewpoint of the photosensitive properties, water absorption and availability of the resulting polymer, phthalic anhydride or trimellitic acid is desirable, and from the viewpoint of polymer synthesis. Mellitic acid anhydride is more desirable.

<(B) component>
The photoacid generator (B) has a function of generating acid directly or jointly by irradiation of light used for exposure or the like and increasing the solubility of the light irradiated portion in an alkali developer. For example, the type and structure are not particularly limited. Moreover, a photo-acid generator can also be used 1 type or in combination of 2 or more types.

  As the photoacid generator of the component (B), any of the conventionally known photoacid generators can be applied, and specific examples thereof include o-quinonediazide compounds, allyldiazonium salts, diallyliodonium salts, triallylsulfonium. Examples thereof include salts, o-nitrobenzyl esters, p-nitrobenzyl esters, trihalomethyl group-substituted s-triazine derivatives, and imide sulfonate derivatives.

  Moreover, a sensitizer can be used together with the photo-acid generator of (B) component as needed. Examples of such sensitizers include, but are not limited to, perylene, anthracene, thioxanthone, Michler ketone, benzophenone, fluorene, and the like.

Among the photoacid generators of the component (B), an o-quinonediazide compound is desirable from the viewpoint that high sensitivity and high resolution can be obtained in a coating film obtained using a positive photosensitive resin composition.
The o-quinonediazide compound is usually obtained by a condensation reaction of o-quinonediazidesulfonyl chloride with a compound having at least one group selected from a hydroxy group and an amino group in the presence of a basic catalyst. Obtained as an acid ester or o-quinonediazidesulfonamide.

  Examples of the o-quinonediazide sulfonic acid component constituting the o-quinonediazidesulfonyl chloride include 1,2-naphthoquinone-2-diazide-4-sulfonic acid and 1,2-naphthoquinone-2-diazide-5-sulfonic acid. 1,2-naphthoquinone-2-diazide-6-sulfonic acid and the like.

Specific examples of the compound having a hydroxy group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, o-methoxyphenol, 4,4-isopropylidenediphenol, 1,1- Bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxyphenylsulfone, 4,4-hexafluoroisopropylidenediphenol, 4,4 ′, 4 ″ -trihydroxytriphenylmethane, 1,1,1- Tris (4-hydroxyphenyl) ethane, 4,4 ′-[1
-[4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, methyl 3,4,5-trihydroxybenzoate, propyl 3,4,5-trihydroxybenzoate, 3 , 4,5-trihydroxybenzoic acid isoamyl ester, 3,4,5-trihydroxybenzoic acid-2-ethylbutyl ester, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2 ′ , 4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, phenol compounds such as 2,3,4,2 ', 4'-pentahydroxybenzophenone, ethanol, 2-propanol, 4, -Butanol, cyclohexanol, ethylene glycol, propylene glycol, polyethylene Glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate, include aliphatic alcohols such as butyl lactate.

  Examples of the compound having an amino group include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, Examples thereof include anilines such as 4,4′-diaminodiphenylmethane and 4,4′-diaminodiphenyl ether, and aminocyclohexane.

  Furthermore, specific examples of the compound having both a hydroxy group and an amino group include o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2,3-diaminophenol, and 2,4-diamino. Phenol, 4,4′-diamino-4 ″ -hydroxytriphenylmethane, 4-amino-4 ′, 4 ″ -dihydroxytriphenylmethane, bis (4-amino-3-carboxy-5-hydroxyphenyl) ether Bis (4-amino-3-carboxy-5-hydroxyphenyl) methane, bis (4-amino-3-carboxy-5-hydroxyphenyl) sulfone, 2,2-bis (4-amino-3-carboxy-5) -Hydroxyphenyl) propane, 2,2-bis (4-amino-3-carboxy-5-hydroxyphenyl) Sulfonyl) amino phenols such as hexafluoropropane, 2-aminoethanol, 3-aminopropanol, mention may be made of alkanolamines, such as 4-amino-cyclohexanol.

  When the o-quinonediazidosulfonyl chloride and a compound having at least one selected from a hydroxy group and an amino group are subjected to a condensation reaction, a part or all of the hydroxy group or amino group of the compound is o-quinonediazidesulfonyl chloride o-quinonediazide A disubstituted, trisubstituted, tetrasubstituted or pentasubstituted o-quinonediazide compound substituted with a sulfonyl group is obtained. When such an o-quinonediazide compound is used as one component of a positive photosensitive resin composition, the above-mentioned polysubstituted o-quinonediazide compound alone or two or more polysubstituted selected from the above polysubstituted products is used. Generally used as a mixture of bodies.

  Among the o-quinonediazide compounds described above, the coating residue obtained using the positive photosensitive resin composition has a good balance of difference in development solubility between the exposed and unexposed areas, and the development residue at the bottom of the pattern during development From the viewpoint that there is no (residue at the pattern edge part), o-quinonediazide sulfonic acid ester of p-cresol, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] Phenyl] ethylidene] bisphenol o-quinonediazide sulfonate, methyl 3,4,5-trihydroxybenzoate o-quinonediazide sulfonate, 2,3,4-trihydroxybenzophenone o-quinonediazide sulfonate, or O-Quinonediazi of 2,3,4,4'-tetrahydroxybenzophenone Sulfonic acid ester is preferable, be used those compounds singly, or may be mixed and used as the two or more selected arbitrarily from these compounds.

  The content of the photoacid generator as the component (B) used in the present invention is 0.01 to 100 parts by mass based on 100 parts by mass of the component (A). In the coating film obtained from the positive photosensitive resin composition of the present invention, the balance of the developer solubility difference between the exposed area and the unexposed area is improved, and further, the sensitivity of the coating film and the coating film obtained from the coating film are obtained. From the viewpoint of the mechanical properties of the cured film to be obtained, the content of the photoacid generator as the component (B) is particularly preferably 50 parts by mass or less, and more preferably 30 parts by mass or less.

<(C) component>
As the solvent (C) used in the positive photosensitive resin composition of the present invention, the solubility of the component (A) (polyimide precursor having a structural unit represented by formula (1) or polyimide obtained therefrom) is high. Point, good compatibility with the component (B) (photoacid generator) and other components described later, easy handling in the positive photosensitive resin composition, and low pollution organic From the viewpoint of being a solvent, alcohols or alkyl esters having 4 or more carbon atoms are desirable.

  Typical solvents include butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, γ-butyrolactone, n-butanol, sec-butanol, t-butanol, methoxymethylpentanol, and methyl cellosolve. , Ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, butyl carbitol acetate, ethyl carbitol, ethyl carbitol acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, dipropylene glycol monoacetate monomethyl ether, Dipropylene glycol monoethyl ether, dipropylene glycol Monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 2-ethoxyethanol, 2-butoxyethanol, methyl lactate, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, n-acetate Butyl, hexyl acetate, methyl 2-hydroxyisobutyrate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3 -Propyl methoxypropionate, butyl 3-methoxypropionate or butyl butyrate. These solvents may be two or more kinds of mixed solvents.

  In particular, from the viewpoint of easy handling in the positive photosensitive resin composition, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, methyl 2-hydroxyisobutyrate, γ-butyrolactone, and lactic acid It is desirable to use one or a mixture of two or more selected from the group consisting of butyl. Further, from the viewpoint of storage stability of the positive photosensitive resin composition, it is selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, methyl 2-hydroxyisobutyrate, and γ-butyrolactone. One or a mixture of two or more is desirable, and from the viewpoint of photosensitive properties, one or two or more selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl 2-hydroxyisobutyrate, and γ-butyrolactone Mixtures are desirable.

  In addition to the above solvents, acetone, methanol, ethanol, isopropyl alcohol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, ethylene glycol, ethylene glycol monoacetate, propylene glycol, diethylene glycol , Diethylene glycol monoacetate, diethylene glycol dimethyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl ether, diisobutyl ketone , Methylcyclohexene, propyl ether, dihexyl ether Ter, dioxane, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-vinylpyrrolidone, dimethyl sulfoxide, N-methylpyrrolidone, n-hexane, n-pentane, n- A solvent such as octane, 2-methoxyethanol, diethyl ether, cyclohexanone, 3-ethoxypropionic acid, 3-methoxypropionic acid or diglyme may be mixed and used. However, from the viewpoint that these other solvents are used in conventional positive photosensitive resin compositions (not low-pollution organic solvents), the amount of these solvents used is preferably as small as possible, preferably in the overall solvent ratio. 5 mass% or less, More preferably, it is 1 mass% or less.

<(D) component>
The positive photosensitive resin composition of the present invention can contain a maleimide compound as the component (D). The maleimide compound of component (D) is not particularly limited as long as it is a compound that is soluble in an alkali developer in the development step of a coating film obtained using the positive photosensitive resin composition of the present invention. The maleimide compound of component (D) is not particularly limited as long as the maleimide moiety is directly connected to the aromatic ring and the hydrogen atom is directly connected to the adjacent aromatic carbon.

  Examples of the maleimide compound having a structure in which a maleimide moiety is directly connected to an aromatic ring and a hydrogen atom is directly connected to an adjacent aromatic carbon include a compound represented by the following formula (10).

In the above formula (10), R ³³ represents a divalent group, and R ^{34 to} R ⁴³ each independently represents a hydrogen atom or an organic group having 1 to 12 carbon atoms.

In particular, in the formula (10), it is desirable to use a maleimide compound in which R ³³ has a structure represented by the following formula (11) as the component (D).

In the above formula (11), l and k each independently represent 0 or 1, and R ^{44 to} R ⁴⁶ each independently represent an organic group having 1 to 12 carbon atoms, an oxygen atom, a sulfur atom, or nitrogen Represents a divalent group having an atom.
In particular, in the formula (11), it is desirable that l and k are 1, R ⁴⁴ and R ⁴⁶ are oxygen atoms, and R ⁴⁵ represents a dimethylmethylene group.

Specific examples of the maleimide compound of the component (D) represented by the above formula (10) include 2,2-bis (3-amino-4-maleimide) hexafluoropropane, 4,4′-dimaleimide diphenyl ether, 3, 4'-dimaleimide diphenyl ether, 3,3'-dimaleimide diphenyl ether, 4,4'-dimaleimide diphenyl sulfide, 4,4'-dimaleimide diphenylmethane, 3,4'-dimaleimide diphenylmethane, 3,3'-di Maleimide diphenylmethane, 4,4-methylene-bis (2-methylmaleimide), 4,4′-dimaleimidodiphenylsulfone, 3,3′-dimaleimidodiphenylsulfone,
, 4′-bis (4-maleimidophenoxy) benzene, 1,3′-bis (4-maleimidophenoxy) benzene, 1,3′-bis (4-maleimidophenoxy) benzene, bis [4- (4-maleimidophenoxy) ) Phenyl] sulfone, bis [4- (3-maleimidophenoxy) phenyl] sulfone, bis [3- (4-maleimidophenoxy) phenyl] sulfone, bis [3- (3-maleimidophenoxy) phenyl] sulfone, 2,2 Examples thereof include, but are not limited to, compounds such as' -bis [4- (4-maleimidophenoxy) phenyl] propane and 2,2-bis [4- (3-aminophenoxy) phenyl] propane.
Of the above compounds, 4,4′-dimaleimidodiphenylmethane and 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane are desirable from the viewpoint of easy availability, and further from the viewpoint of photosensitive properties. 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane is more preferable.
The maleimide compound of component (D) in the present invention can be used in combination of two or more.

  The content of the maleimide compound of component (D) in the positive photosensitive resin composition of the present invention is not particularly limited, but is preferably 5 to 100 parts by weight based on 100 parts by weight of the polyimide precursor of component (A). It is more desirable to be 20 to 20 parts by mass.

<(E) component>
The positive photosensitive resin composition of the present invention can further contain an isocyanuric compound as the component (E). The isocyanuric compound as the component (E) is not particularly limited as long as it is a compound that is soluble in an alkaline developer in the developing step of a coating film obtained using the positive photosensitive resin composition of the present invention.
Specific examples include compounds represented by the following formula (12).

In the above formula, R ^{47 to} R ⁴⁹ each independently represents an organic group having a structure of an epoxy group, an oxetane group, a urethane group, an allyl group, or an acrylic group.

In particular, in the above formula (12), R ^{47 to} R ⁴⁹ are preferably any groups represented by the following formulas (13) to (15).

In the above formulas, R ^{50 to} R ⁵⁸ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, atom, a nitro group, a formyl group, a cyano group, a carboxyl group, a phospho group, a sulfo group, an optionally substituted phenyl group W ^4, W ⁴ optionally substituted by a naphthyl group, optionally substituted with W ⁴ It represents a thienyl group which may be substituted or a furyl group which may be substituted with W ⁴ .
W ⁴ is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group Represents a group, a phospho group or a sulfo group.

Specific examples of the (I) component isoasianuric compound represented by the above formula (12) include isocyanuric epoxy compounds such as diallyl glycidyl isocyanuric acid, monoallyl diglycidyl isocyanuric acid, triglycidyl isocyanuric acid, A-9300, A And ethoxylated isocyanuric triacrylate manufactured by -9300-Cl (manufactured by Shin-Nakamura Chemical Co., Ltd.). Of the above-mentioned compounds, diallyl glycidyl isocyanuric acid, monoallyl diglycidyl isocyanuric acid, A-9300 and A-9300-Cl are preferable from the viewpoint of solubility and photosensitivity, and monoallyl diglycidyl from the viewpoint of storage stability. Isocyanuric acid, A-9300 and A-9300-Cl are more preferred.
The isocyanuric compound of component (E) in the present invention can be used in combination of two or more.

  The content of the component (E) isocyanuric compound in the positive photosensitive resin composition of the present invention is not particularly limited, but is preferably 3 to 100 parts by weight based on 100 parts by weight of the polyimide precursor (A). From the viewpoint of characteristics, the content is more preferably 5 to 50 parts by mass.

<Other additives>
Furthermore, the positive type photosensitive resin composition of the present invention can be used as necessary, as long as the effects of the present invention are not impaired, as a surfactant, a rheology modifier, an adhesion aid such as a silane coupling agent, a pigment, and a dye. , A storage stabilizer, an antifoaming agent, or a dissolution accelerator such as polyhydric phenol and polycarboxylic acid can be contained.

Examples of the surfactant that can be used for the purpose of improving the coating property of the positive photosensitive resin composition of the present invention include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surfactant. As this type of surfactant, for example, commercially available products such as those manufactured by Sumitomo 3M Co., Ltd., Dainippon Ink Chemical Co., Ltd., or Asahi Glass Co., Ltd. can be used. These commercial products are convenient because they can be easily obtained. Specific examples include F-top EF301, EF303, EF352 (manufactured by Gemco), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink & Chemicals, Inc.), Florard FC430, FC431 (Sumitomo) 3M), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.), FTX-206D, FTX-212D, FTX-218, FTX-220D Fluorine surfactants such as FTX-230D, FTX-240D, FTX-212P, FTX-220P, FTX-228P, FTX-240G, etc.
The said surfactant can be used individually by 1 type or in combination of 2 or more types.
When a surfactant is used, its content is usually 0.1 to 1.0% by mass in 100% by mass of the positive photosensitive resin composition, and is preferably 0 from the viewpoint of storage stability. .5 to 1.0% by mass. When the amount of the surfactant used exceeds 1.0% by mass, bubbles are likely to be mixed in the varnish (positive photosensitive dendritic composition), and the effect of improving the coating property becomes dull, which is not economical. .

<Positive photosensitive resin composition>
The positive photosensitive resin composition of the present invention contains (A) component polyimide, (B) component photoacid generator and (C) solvent, and (D) component maleimide compound, E) It is a composition that can further contain one or more other components such as an isocyanuric compound and a surfactant.

Among these, preferred examples of the positive photosensitive resin composition of the present invention are as follows.
[1]: A positive photosensitive resin composition containing 0.01 to 100 parts by mass of the component (B) based on 100 parts by mass of the component (A) and dissolving these components in the solvent (C).
[2]: A positive photosensitive resin composition further containing 5 to 100 parts by mass of the component (D) based on 100 parts by mass of the component (A) in the composition of the above [1].
[3]: A positive photosensitive resin composition further containing 3 to 100 parts by mass of component (E) based on 100 parts by mass of component (A) in the composition of [2] above.

  The ratio of the solid content in the positive photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but generally the solid content concentration is 1 to 50% by mass. A coating film can be easily formed by forming a solution of a positive photosensitive resin composition having a concentration arbitrarily selected from the range. Here, solid content means what remove | excluded the (C) solvent from all the components of the positive photosensitive resin composition.

  The method for preparing the positive photosensitive resin composition of the present invention is not particularly limited. Since this type of composition is usually used in the form of a solution, the positive photosensitive resin composition of the present invention generally comprises the component (A), the component (B), and the component (D) as desired. Examples include a method of dissolving the component (E) in the solvent (C) to obtain a uniform solution, or a method in which other additives are further added and mixed at an appropriate stage of the preparation method.

  In preparing the positive photosensitive resin composition of the present invention, the component (A) is produced, that is, a component selected from tetracarboxylic acid and its derivative and a diamine component are polymerized in an organic solvent to obtain an imide. The reaction solution obtained by conversion can be used as it is. In addition, as an organic solvent used at this time, the solvent described in the above-mentioned (C) solvent is mentioned. In this case, when the component (B) is added to the reaction solution of the component (A) to obtain a uniform solution, the solvent (C) may be additionally added for the purpose of adjusting the concentration. At this time, the organic solvent used at the time of manufacture of (A) component and the (C) solvent used for density | concentration adjustment may be the same, and may differ.

Moreover, when using a plurality of types of organic solvents, not only a plurality of types of organic solvents are mixed and used first, but also a plurality of types of organic solvents can be added separately.
Thus, the prepared positive photosensitive resin composition solution is preferably used after being filtered using a filter having a pore diameter of about 0.2 μm.

<Coating film and cured film>
In general, for example, the positive photosensitive resin composition of the present invention is made of an ITO substrate, a silicon wafer, a glass plate, a ceramic substrate, an oxide film, a nitride film, or the like by a known method such as spin coating, dipping, or printing. A coating film made of the positive photosensitive resin composition of the present invention can be formed by coating on the material and then preliminary drying at a temperature of 60 ° C. to 160 ° C., preferably 70 ° C. to 130 ° C.

  After the coating film is formed, the coating film is exposed using a mask having a predetermined pattern, for example, with ultraviolet light, and developed with an alkali developer, whereby the exposed portion is washed away, thereby sharpening the end face (clear) A relief pattern is formed on the substrate.

The alkaline developer used here is not particularly limited as long as it is an alkaline aqueous solution. For example, an aqueous solution of an alkali metal hydroxide such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, tetramethylammonium hydroxide, or the like. And aqueous solutions of quaternary ammonium hydroxides such as tetraethylammonium hydroxide and choline, and aqueous amine solutions such as ethanolamine, propylamine and ethylenediamine.
The concentration of the alkaline developer is generally 10% by mass or less, and an industrial aqueous solution of 0.1 to 3.0% by mass is used industrially. The alkaline developer can also contain alcohols or surfactants, and these are preferably contained in an amount of about 0.05 to 10% by mass.

  In the development step, the temperature of the alkali developer can be arbitrarily selected. However, when the positive photosensitive resin composition of the present invention is used, the exposed portion is highly soluble, so that the alkali development can be easily performed at room temperature. Development with a liquid can be performed.

  A relief pattern having low water absorption, excellent electrical characteristics, and good heat resistance and chemical resistance by heat-treating (baking) the substrate having the relief pattern thus obtained at a temperature of 180 ° C. to 400 ° C. The cured film which has can be obtained.

  Since the cured film obtained from the positive photosensitive resin composition of the present invention has such excellent effects, it can be used for electric / electronic devices, semiconductor devices, display devices, and the like. In particular, a cured film obtained from the positive photosensitive resin composition of the present invention has a characteristic effect that the reliability of an organic EL element (a kind of LED (Light-Emitting Diode) element) is high, and thus a light-emitting element It is very useful as an insulating film and partition material for organic EL elements, where damage to the metal is a major problem, or for buffer coating where the ion migration of copper wiring is greatly affected by the water absorption of the insulating film in semiconductor packages. is there.

  The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

[Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.
<Diamine component>
BAHF: 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane BATF: 2,2′-bis (3-amino-4-toluyl) hexafluoropropane ODA: 4,4′-diaminodiphenyl ether DDM: 4,4′-diaminodiphenylmethane APDS: bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane DBA: 1,3-diamino-5-carboxybenzene TFMB: 2,2′- Bis (trifluoromethyl) benzidine <Tetracarboxylic acid component>
DSDA: 3,3′-4,4′-diphenylsulfonetetracarboxylic anhydride 6FDA: 4,4′-hexafluoroisopropylidenediphthalic anhydride PMDA: pyromellitic anhydride ODPA: 3,3 ′, 4 , 4'-Diphenyl ether tetracarboxylic anhydride
<End sealant>
T MA: trimellitic anhydride <solvent>
PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether HBM: Methyl 2-hydroxyisobutyrate NMP: N-methylpyrrolidone γ-BL: γ-butyrolactone <Photoacid generator>
P200: manufactured by Toyo Gosei Kogyo Co., Ltd. P-200 (trade name) 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1methylethyl] phenyl] ethylidene] bisphenol 1 mol and 1 , 2-naphthoquinone-2-diazide-5-sulfonyl chloride, a photosensitizer synthesized by a condensation reaction <maleimide compound>
BMI-80: 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane BMI-2300: Phenylmethanemaleimide oligomer, manufactured by Daiwa Kasei Kogyo Co., Ltd. <Isocyanur compound>
TEPIC: Tris- (2,3-epoxypropyl) -isocyanurate, manufactured by Nissan Chemical Industries, Ltd., trade name Tepic DAMEICA: diallyl glycidyl isocyanuric acid MADEICA: monoallyl diglycidyl isocyanuric acid A-9300: ethoxylated isocyanuric acid tri Acrylate, Shin-Nakamura Chemical Co., Ltd. A-9300-Cl: Ethoxylated isocyanuric acid triacrylate, Shin-Nakamura Chemical Co., Ltd. <Surfactant>
Megafuck R-30: Dainippon Ink & Chemicals Co., Ltd. Footgent (FTX) 212D: Neos Co., Ltd.

[Measurement of number average molecular weight and weight average molecular weight]
In accordance with the following synthesis examples, the weight average molecular weight (hereinafter abbreviated as Mw) and molecular weight distribution of the polymer were measured using GPC apparatus (Shodex (registered trademark) columns KF803L and KF805L) manufactured by JASCO Corporation and dimethylformamide as the elution solvent. The measurement was performed under the condition that the column was eluted at a flow rate of 1 ml / min (column temperature: 50 ° C.). Mw is expressed in terms of polystyrene.

[Measurement of imidization rate]
The imidation ratio was calculated from the proton ratio of the aromatic skeleton of the polymer skeleton and the proton ratio of the NH moiety of the polyamic acid by measuring H-NMR using an NMR apparatus (JNM-LA series, manufactured by JEOL Ltd.). .

[Synthesis example]
<Production of polyimide solution (Synthesis Example 1)>
After 69.6 g (0.188 mol) of BAHF and 5.21 g (0.0021 mol) of APDS were dissolved in 350 g of NMP, 67.6 g (0.188 mol) of DSDA was added and stirred at 23 ° C. for 6 hours. Thereafter, 150 g of acetic acid was added and reacted at 80 ° C. for 20 hours. Thereafter, 8.06 g (0.0042 mol) of TMA was added and stirred at 23 ° C. for 24 hours.
The obtained polymer had an Mw of 8,400 and a molecular weight distribution of 1.77.
This polymer solution was precipitated in about 6 times amount of 50% by mass aqueous methanol solution (4000 g), and the precipitate was dried under reduced pressure to obtain polyimide powder (yield: 91%, imidation rate: 92%).
50 g of the polymer powder was dissolved in 100 g of PGMEA, and 1.00 g of the obtained polymer solution was transferred to an aluminum cup and heated on a hot plate for 2 hours to calculate the solid content concentration of the polymer solution (solid content concentration: 32.5% by mass).
The obtained polymer was soluble in PGME and PGMEA.

<Production of polyimide solution (Synthesis Example 2 )>
After dissolving 138.7 g (0.378 mol) of BAHF, 5.23 g (0.0021 mol) of APDS and 4.21 g (0.0021 mol) of ODA in 700 g of NMP, 135.7 g (0.379 mol) of DSDA was dissolved. And 16.2 g (0.084 mol) of TMA were added and stirred at 23 ° C. for 6 hours, and then 150 g of acetic acid was added and reacted at 80 ° C. for 20 hours.
Mw of the obtained polymer was 10,100 and molecular weight distribution was 1.88.
This polymer solution was subjected to precipitation drying in the same manner as in Synthesis Example 1 to obtain a polyimide powder (yield: 90%, imidization rate: 90%).
50 g of the polymer powder was dissolved in 100 g of HBM, and 1.00 g of the obtained polymer solution was transferred to an aluminum cup and heated on a hot plate for 2 hours to calculate the solid content concentration of the polymer solution (solid content concentration). : 33.1% by mass).
The obtained polymer was soluble in HBM.

<Manufacture of various polyamic acid solutions (Synthesis Examples 3 to 6 )>
Various diamines and acid dianhydrides were dissolved in PGME so as to have a concentration of 15% by mass, and a polymer was synthesized using the same method as in Synthesis Example 2. Table 1 shows the amount of diamine, acid dianhydride, and solvent used, the Mw and molecular weight distribution of the obtained polymer, the solid content concentration of the obtained polymer solution, and the imidization rate.
The obtained polymer was soluble in PGME.

<Production of polyamic acid solution (Synthesis Example 7 )>
An acid dianhydride was added to NMP in which various diamines were dissolved and reacted for 4 hours to synthesize a polymer. Thereafter, 50 g of the reaction solution was added to 1000 ml of pure water, and the precipitate was filtered and dried under reduced pressure to obtain polyamic acid. Table 1 shows the diamine, acid dianhydride, the amount of the solvent used, the Mw and molecular weight distribution of the obtained polymer, the solid content concentration, and the imidization rate. Since the obtained polymer was insoluble in either PGME or PGMEA, the reaction solution was used as it was for the preparation of the positive photosensitive resin composition described later.
As in Synthesis Example 1, as a result of synthesizing the polymer in PGME in which various diamines were dissolved, the polymer was precipitated in 1 hour after the reaction.

[Production of Positive Photosensitive Resin Composition: Examples 1 to 7 and Comparative Examples 1 to 5]
According to the composition shown in the following Table 2 and Table 3, (A) component, (B) component, (C) solvent, (D) component, (E) component, and fluorine-type surfactant (Dainippon Ink and Chemicals ( Co., Ltd., MegaFac R-30, or Neos Co., Ltd. (FTX) 212D) is mixed at a predetermined ratio and stirred at room temperature for 3 hours or more to obtain a uniform solution. A positive photosensitive resin composition of each example and each comparative example was prepared.

[Photosensitive characteristic evaluation: Examples 1 to 7 , Comparative Examples 1 to 5]
The photosensitive characteristics of the obtained positive photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 5 were evaluated by the following method. Table 4 shows the obtained results.

<1. Film thickness before heat treatment (firing)>
The positive photosensitive resin composition is applied onto an ITO substrate (manufactured by Yamato Vacuum Industry Co., Ltd.) having a step of 25 mm × 25 mm using a spin coater, and then pre-baked on a hot plate at a temperature of 100 ° C. for 120 seconds. A film was formed. The film thickness was measured using a contact-type film thickness measuring device (Dektak 3ST manufactured by ULVAC).

<2. Film thickness after development, resolution (line width)>
The obtained coating film was passed through a line / space mask of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 μm. Ultraviolet light was irradiated for 11 seconds (70 mJ / cm ² ) by an ultraviolet irradiation device PLA-501 manufactured by Canon Inc. After the exposure, the film was immersed in a tetramethylammonium hydroxide aqueous solution at 23 ° C. (the concentration of the aqueous solution used in each example is described in Table 4) for 30 seconds for development, and the film thickness after development was measured.
Moreover, the coating film after image development was observed with the optical microscope, and the minimum line | wire width in which the line / space was formed without pattern peeling was made into the resolution.

<3. Film thickness after heat treatment (firing)>
<2. > Was heated at 230 ° C. for 30 minutes, and the film thickness was measured.

<4. Element characteristic evaluation: Examples 1 to 7 and Comparative Examples 1 to 5>
<1. > The ultraviolet light was irradiated for 11 seconds (70 mJ / cm < ² >) with the ultraviolet irradiation apparatus PLA-501 by Canon Inc. through the mask of the line / space of 100 micrometers / 200 micrometers. After the exposure, development was performed by immersing in an aqueous solution of tetramethylammonium hydroxide at 23 ° C. (the concentration of the aqueous solution used in each example is described in Table 4) for 30 seconds, and heating at 230 ° C. for 30 minutes to obtain a polyimide pattern. .
The obtained polyimide pattern (Comparative Example 5 was dissolved on the stepped ITO substrate because the entire pattern was dissolved after development, and a polyimide film was obtained without development.) UV ozone cleaning device (manufactured by Technovision Co., Ltd.) ) For 40 minutes, and after that, ND-1032 (Nissan Chemical Industry Co., Ltd.) was applied by spin coating and heat-treated (fired) at 200 ° C. for 1 hour on a hot plate to form a 30 nm thick film. Obtained. Then, 15 mm ² squares were scraped off from the center, and α-NPD, Alq3, FLi, and Al were deposited in this order as device components under vacuum conditions to produce devices. The vapor deposition component was measured with a crystal vibration film formation controller CRTM-6000 (manufactured by Nippon Vacuum Technology Co., Ltd.). Thereafter, a current of 9 V was applied to the device, and the light emitting surface was observed with an optical microscope. Table 5 shows the element components, the deposition amount, and the observation evaluation results of the light emitting surface.

[Element evaluation results]
In the element using P1 or P2 , clear light emission was also observed at the polyimide pattern edge portion. This indicates that the partition element obtained by using the positive photosensitive resin compositions of Examples 1 to 7 can produce pixels without adversely affecting the light emitting surface. It was.
On the other hand, in the element using HP1 to HP5, there was a shadow or blur at the interface between the polyimide pattern edge portion and the light emitting surface, and a light emission failure was observed. That is, when the positive type photosensitive resin compositions of Comparative Examples 1 to 5 using these polyimides were used for device fabrication, it was feared that the resulting device would cause a defective light emitting surface. In addition, although the element using HP4 was a result that a blur exists in a part of interface of an edge part and a light emission surface, it is a result (50 micrometers) that resolution is low as shown in Table 4, and a fine pattern of As a result, it was determined that it was unsuitable for the production of an organic EL element which requires formation.

Claims (23)

A positive photosensitive resin containing a polyimide represented by the following formula (1) as the component (A) and a compound that generates an acid by light as the component (B), which are dissolved in the solvent (C). Composition.

(In the formula, X represents a tetravalent aliphatic group or an aromatic group,
Y represents a divalent organic group containing an aromatic group substituted with at least one OH group;
Z ¹ and Z ² represent a group represented by the following formula (2), or a group represented by the following formula (4) by combining Z ¹ and Q ¹ or Z ² and Q ² together. Forming,

Q ¹ represents a hydrogen atom, or together with adjacent Z ¹ forms a ring structure,
Q ² represents a hydrogen atom, or together with the adjacent Z ¹ forms a ring structure,
m represents an integer of 1 or more. ) The positive photosensitive resin composition according to claim 1, wherein Y is a divalent organic group containing a benzene ring substituted with at least one OH group. The positive photosensitive resin composition according to claim 1 , wherein Y is a divalent organic group containing two or more benzene rings substituted with at least one OH group. Wherein Y comprises at least one structure selected from the group consisting of structures represented by the following formula (5) to (7), according to any one of claims 1 to 3 Positive photosensitive resin composition.

(Wherein R ^{1 to} R ²⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, Atom, nitro group, formyl group, cyano group, carboxyl group, phospho group, sulfo group, phenyl group optionally substituted with W, naphthyl group optionally substituted with W, optionally substituted with W Represents a thienyl group or a furyl group optionally substituted by W;
W is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, or a carboxyl group. Represents a phospho group or a sulfo group,
Z ^{1 to} Z ⁶ are a single bond, an alkylene group having 1 to 10 carbon atoms which may be substituted with W ¹ , —C (O) O—, —C (O) NH—, —O—, — S—, —S (O) ₂ — or —C (O) —
W ¹ represents an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms,
p to x represent an integer of 1 or more, and 2 ≧ p + q ≧ 1, 3 ≧ r + s + t ≧ 1, 4 ≧ u + v + w + x ≧ 1. ) Z ^{3 to} Z ⁷ are a single bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —C (O) NH—, —O—, —S (O The positive photosensitive resin composition according to any one of claims 1 to 4 , which represents _2- or -C (O)-. The component (A) is a polyimide containing at least one structure represented by the following formula (9) in addition to the repeating unit structure represented by the formula (1) and the both terminal structures. The positive photosensitive resin composition as described in any one of thru | or 5 thru | or 5 .

(Where
R ^{29 to} R ³² are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, or a nitro group. , formyl group, a cyano group, a carboxyl group, a phospho group, a sulfo group, a phenyl group which may be substituted with W ^2, a naphthyl group which may be substituted with W ^2, which may be substituted with W ^2-thienyl Represents a furyl group optionally substituted by a group or W ² ,
W ² is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group Represents a group, a phospho group or a sulfo group,
Z ^{7 to} Z ⁹ are each independently a single bond, an alkylene group having 1 to 10 carbon atoms which may be substituted with W ³ , —C (O) O—, —C (O) NH—, -O-, -S-, -S (O) _2- or -C (O)-
W ³ represents an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and
q represents an integer of 1 or more. ) In the above formula ^{(9), R 29} to ^{R 32} represent a methyl group, ^{Z 7} represents -O-, ^{Z 8} to Z ⁹ represents a propylene group, positive photosensitive resin composition according to claim 6 object. Wherein the component (A) is a polyimide obtained from the polyimide precursor obtained by polymerizing a tetracarboxylic acid component and a diamine component containing a compound represented by the following formula (8), according to claim 1 to claim 7 The positive photosensitive resin composition as described in any one of these.

(In the formula, R ²⁸ represents a divalent group having a sulfur atom.) The positive photosensitive resin composition according to claim 8 , wherein the compound represented by the formula (8) accounts for 40 to 99 mol% in the tetracarboxylic acid component. The positive photosensitive resin composition according to claim 8 or 9 , wherein, in the formula (8), R ²⁸ is a divalent group having a sulfonyl group. The positive photosensitive resin composition according to any one of claims 1 to 10 , wherein the component (B) is a naphthoquinone diazide sulfonic acid ester compound. The positive photosensitive resin according to any one of claims 1 to 11 , wherein the solvent (C) is at least one selected from the group consisting of alcohols having 4 or more carbon atoms, or alkyl esters. Resin composition. The positive photosensitive resin composition according to any one of claims 1 to 12 , comprising 0.01 to 100 parts by mass of the component (B) based on 100 parts by mass of the component (A). object. The positive photosensitive resin composition according to claim 13 , further comprising 5 to 100 parts by mass of the maleimide compound represented by the following (10) as the component (D) based on 100 parts by mass of the component (A). .

(In the formula, R ³³ represents a divalent group, and R ^{34 to} R ⁴³ each independently represents a hydrogen atom or an organic group having 1 to 12 carbon atoms.) The positive photosensitive resin composition according to claim 14 , wherein, in the formula (10), R ³³ has a structure represented by the following formula (11).

(Wherein l and k each independently represent 0 or 1, and R ^{44 to} R ⁴⁶ each independently represent a divalent organic group having 1 to 12 carbon atoms, an oxygen atom, a sulfur atom, or Represents a divalent group having a nitrogen atom.) The positive photosensitive resin composition according to claim 15 , wherein in the formula (11), l and k represent 1, R ⁴⁴ and R ⁴⁶ represent an oxygen atom, and R ⁴⁵ represents a dimethylmethylene group. Containing 3 to 100 parts by weight based on 100 parts by weight of the further component (A) an isocyanuric compound represented by the following formula (12) as component (E), any one of claims 13 to claim 16 The positive photosensitive resin composition according to one item.

(In the formula, R ^{47 to} R ⁴⁹ each independently represents an organic group having a structure of an epoxy group, an oxetane group, a urethane group, an allyl group, or an acrylic group.) The positive photosensitive resin composition according to claim 17 , wherein in the formula (12), R ^{46 to} R ⁴⁸ are any groups represented by the following formulas (13) to (15).

(Wherein R ^{50 to} R ⁵⁸ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, atom, a nitro group, a formyl group, a cyano group, a carboxyl group, a phospho group, a sulfo group, an optionally substituted phenyl group W ^4, W ⁴ optionally substituted by a naphthyl group, optionally substituted with W ⁴ An optionally substituted thienyl group or a furyl group optionally substituted by W ⁴ ;
W ⁴ is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group Represents a group, a phospho group or a sulfo group. ) A cured film obtained using the positive photosensitive resin composition according to any one of claims 1 to 18 . An electronic component having the cured film according to claim 19 . An organic EL device having the cured film according to claim 19 . A method for forming a relief pattern, wherein the positive photosensitive resin composition according to any one of claims 1 to 18 is applied on a substrate, dried by heating, and then developed by irradiation with ultraviolet rays. Following formula (1)

(In the formula, X represents a tetravalent aliphatic group or an aromatic group,
Y represents a divalent organic group containing an aromatic group substituted with at least one OH group;
Z ¹ and Z ² are a group represented by the following formula (2) , or a group represented by the following formula (4) by combining Z ¹ and Q ¹ or Z ² and Q ² together. Forming,

Q ¹ represents a hydrogen atom, or together with adjacent Z ¹ forms a ring structure,
Q ² represents a hydrogen atom or together with adjacent Z ² forms a ring structure,
m represents an integer of 1 or more. )
Polyimide represented by