KR101674654B1 - Positive Photosensitive Resin Composition, Cured Film Thereof, and Display Element - Google Patents

Abstract

(식(1) 중, R¹은 식(2)

(식(2) 중, R³은 유황원자를 갖는 유기기를 나타내고, R⁴ 및 R⁵는 각각 독립적으로 수소원자 또는 탄소원자수 1 내지 20의 유기기를 나타낸다.)의 방향족기를 나타내고, R²는 불소원자를 갖는 방향족기를 나타내고, n은 자연수를 나타낸다.)In a display device such as an organic EL device, a positive photosensitive resin composition which is a material for a display element which enables a clear image to be displayed and which is soluble in a low-pollution organic solvent is provided.
(A) a polyimide precursor having a structural unit represented by the following formula (1) or a polyimide obtained therefrom, and (B) a compound capable of generating an acid by light as a component (B) A positive photosensitive resin composition.

, R ¹ (wherein 1 has the formula (2)

(In the formula (2), R ³ represents an organic group having a sulfur atom, R ⁴ and R ⁵ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms), R ² represents fluorine Represents an aromatic group having an atom, and n represents a natural number.)

Description

(Positive Photosensitive Resin Composition, Cured Film Thereof, and Display Element)

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive material favorable to electric and electronic devices, in particular, a surface protecting film, an interlayer insulating film, a passivation film, an electrode protecting layer, etc. of a semiconductor device or a display device. More particularly, the present invention relates to a positive photosensitive resin composition that is soluble in a low-pollution organic solvent and does not cause a poor luminescence on a light-emitting surface when the obtained cured film is used as an insulating film of an organic EL device device, a cured film thereof, ≪ / RTI >

The photosensitive insulating film made of a photosensitive resin typified by a photosensitive polyimide resin having excellent mechanical characteristics and high heat resistance has begun to be widely used not only in the semiconductor field but also in the display field. Particularly, when a photosensitive insulating film is used as a protective film of a thin film transistor (TFT) of a liquid crystal display element or a protective film of an electrode protective film of an organic EL element or the like, it is required to further improve the reliability of the insulating film In addition, from the viewpoint of simplification of the element process, good shape of the protective film, and further productivity, it is required to have properties such as low solubility and solubility in biodegradable solvents. Particularly, in the above-described apparatus, since it is an important condition that display failure is not caused, it is required that the moisture and the photosensitive agent in the cured film entering the final product do not cause defective devices due to penetration.

As a positive photosensitive resin composition that has been proposed so far, there is a polyimide-based positive photosensitive resin composition in which the acidity of polyamic acid is reduced by using a basic organic compound such as triethylamine to suppress the dissolution rate to an alkaline developer Patent Document 1). Further, for the purpose of improving retention of residual film and mechanical strength after heat curing, a positive photosensitive resin composition comprising a polyimide resin and a quinone diazide compound containing a phenolic hydroxyl group and a non-phenolic hydroxy group (Patent Document 2) A resin composition containing a phenolic compound in addition to a polyamide and a diazoquinone compound which are precursors of a polyimide has been proposed for the purpose of improving a high residual film ratio and adhesion to an encapsulating resin (Patent Document 3). Although the materials proposed in these documents are described as having high sensitivity and excellent mechanical properties, there is a fear that the final cured film may be damaged to the element light emitting surface due to penetration of additives (triethylamine, phenolic compound, etc.). As described above, in the conventional positive photosensitive polyimide resin composition, it has been difficult to provide a material satisfying the light emitting property as the partition wall of the light emitting element.

U.S. Patent No. 4880722 Japanese Patent Application Laid-Open No. 2004-94118 Japanese Patent Application Laid-Open No. 9-302221

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a positive photosensitive resin composition which is a display element material capable of displaying a clear image in a display device such as an organic EL device. And to provide a positive photosensitive resin composition dissolved in a low-pollution organic solvent.

The inventor of the present invention has conducted intensive studies to solve the above problems and found the present invention.

That is, as a first aspect, there is provided a polyimide precursor having a structural unit represented by the following formula (1) as a component (A) or a polyimide obtained therefrom, and a compound (B) , And these are dissolved in a solvent (C).

, R ¹ (wherein 1 has the formula (2)

(In the formula (2), R ³ represents an organic group having a sulfur atom, and R ⁴ and R ⁵ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms), R ² Represents an aromatic group having a fluorine atom, and n represents a natural number.)

According to a second aspect, in the positive photosensitive resin composition according to the first aspect, R ³ in the formula (2) is an organic group having a sulfonyl group.

According to a third aspect, in the positive photosensitive resin composition described in the first aspect or the second aspect, at least one of R ⁴ and R ⁵ in the formula (2) is a hydrogen atom.

Fourth aspect, the above formula (1) of, R ² is the following formula (3) having a structure represented by the first aspect to the third positive-type photosensitive resin composition according to any one of the perspectives.

(Wherein R ⁶ represents an organic group of 1 to 8 carbon atoms substituted with a fluorine atom, and X ₁ and X ₂ each independently represent a hydrogen atom, an organic group having 1 to 10 carbon atoms or a hydroxy group.)

According to a fifth aspect, there is provided a polyimide precursor obtained by polymerizing a tetracarboxylic acid component and a diamine component, wherein the component (A) comprises a compound represented by the following formula (4) or a polyimide obtained therefrom, Wherein the positive photosensitive resin composition is a positive photosensitive resin composition.

(Wherein R ⁷ represents an organic group having a sulfur atom).

In a sixth aspect, the tetracarboxylic acid component is at least one compound selected from the group consisting of a tetracarboxylic acid component containing at least one of compounds represented by the following formulas (5) to (8) 5] The positive photosensitive resin composition according to [5].

(Wherein m represents 0 or 1, R ⁸ represents a divalent organic group having 1 to 12 carbon atoms or a divalent organic group having an oxygen atom directly connected to an aromatic ring, and R ⁹ , R ¹⁰ , R ^11, R ¹² and R ¹³ is Each represent an organic group having 1 to 12 carbon atoms.

According to a seventh aspect, in the positive photosensitive resin composition described in the fifth or sixth aspect, the compound represented by the formula (4) accounts for 40 to 99 mol% of the tetracarboxylic acid component.

In a eighth aspect, the positive photosensitive resin composition according to any one of the fifth to seventh aspects is a diamine component containing a diamine compound represented by the following formula (9).

(Wherein R ⁶ represents an organic group having 1 to 8 carbon atoms substituted with a fluorine atom, and X ₃ and X ₄ each independently represent a hydrogen atom, an organic group having 1 to 10 carbon atoms or a hydroxy group.)

In a ninth aspect, the positive photosensitive resin composition according to any one of aspects 5 to 8, wherein the diamine component is a diamine component containing a diaminosiloxane compound.

In a tenth aspect, the positive photosensitive resin composition according to any one of the first to tenth aspects, wherein the component (B) is a naphthoquinonediazide sulfonic acid ester compound.

According to an eleventh aspect, in the positive photosensitive resin composition according to any one of the first to tenth aspects, the solvent (C) is at least one selected from the group consisting of alcohols having 4 or more carbon atoms or alkyl esters.

According to a twelfth aspect, the positive photosensitive resin composition according to any one of the first to eleventh aspects contains 0.01 to 100 parts by mass of the component (B) based on 100 parts by mass of the component (A).

According to a thirteenth aspect, there is provided a positive photosensitive resin composition according to the twelfth aspect, wherein the maleimide compound represented by the following formula (10) is further contained as the component (D) in an amount of 5 to 100 parts by mass based on 100 parts by mass of the component (A) .

(Wherein R ¹⁴ represents a divalent organic group and R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom, Represents an organic group of 1 to 12 in embroidery).

According to a fourteenth aspect, in the positive photosensitive resin composition according to the thirteenth aspect, R ¹⁴ in the formula (10) has a structure represented by the following formula (11).

(Wherein l and k each independently represent 0 or 1, and X ₅ , X ₆ and X ₇ each independently represent a divalent organic group having 1 to 12 carbon atoms, an oxygen atom, a sulfur atom, Lt; / RTI >

In a fifteenth aspect, in the positive photosensitive resin composition according to the fourteenth aspect, in the formula (11), l and k are 1, X ₅ and X ₇ are oxygen atoms, and X ₆ is a dimethylmethyl group.

According to a sixteenth aspect, the positive photosensitive resin composition according to the fifteenth aspect contains the crosslinkable compound as the component (E) in an amount of 5 to 100 parts by mass based on 100 parts by mass of the component (A).

In a seventeenth aspect, a cured film obtained by using the positive photosensitive resin composition according to any one of the first to sixteenth aspects.

In an eighteenth aspect, an electronic part having the cured film according to the seventeenth aspect.

According to a nineteenth aspect, the organic EL device having the cured film according to the eighteenth aspect.

In a twentieth aspect, a positive photosensitive resin composition according to any one of the first to sixteenth aspects is coated on a substrate, heated and dried, and irradiated with ultraviolet light to develop the relief pattern.

[Positive-type photosensitive resin composition]

The positive photosensitive resin composition of the present invention contains a polyimide precursor as component (A), a polyimide obtained therefrom, and a photoacid generator (B), which are dissolved in a solvent (C) A maleimide compound as the component (D), a crosslinking compound as the component (E), and other additives such as a surfactant.

Hereinafter, each component will be described in detail.

≪ Component (A) >

(A) is a polyimide precursor having a structural unit represented by the following formula (1) or a polyimide obtained from the polyimide precursor.

In the formula (1), n represents the degree of polymerization of the polyimide precursor having the structural unit represented by the formula (1) or the polyimide obtained therefrom. Although n is a positive integer, when n is larger than 1000, the solubility in a general organic solvent is extremely lowered, and the viscosity of the resin composition solution remarkably increases, resulting in poor handling properties. Therefore, in consideration of solubility, n is preferably a positive integer of 1000 or less, more preferably a positive integer of less than 100.

Further, since the compound of the component (A) may lower the reliability of the device due to the adsorption of moisture, it is preferable that the compound is imidized within a range that is soluble in the developer. The imidization ratio is preferably 50 to 99.9%, more preferably 60 to 90% from the viewpoint of device reliability and developability.

R ¹ in the formula (1) represents an aromatic group represented by the following formula (2), and in the formula (2), R ³ represents an organic group having a sulfur atom.

In the formula (2), R < ³ > The organic group having a sulfur atom is not particularly limited, but is preferably a sulfonyl group, a sulfide group or a sulfo group from the viewpoints of the solubility of the resulting polymer and the reliability of the device.

In the formula (2), R ⁴ and R ⁵ independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms. In the method of introducing an organic group having 1 to 20 carbon atoms, a polyimide precursor as the component (A) or a polyimide obtained therefrom may be introduced into the monomer in advance, a method of introducing the polymer and a glycidyl group compound or acrylic A method of reacting a compound of the formula (II) or a method of adding a primary amine to the reaction solution to form a salt may be used.

Examples of the organic group having 1 to 20 carbon atoms include an alkyl group, a cycloalkyl group, an aromatic group or an allyl group, and some of these organic groups may be substituted with a halogen group. These organic groups may be any organic group as long as they are soluble in a low-pollution organic solvent, but in view of the solubility of the resulting polymer, a part thereof is preferably substituted with fluorine.

R ² in the formula (1) represents an aromatic group represented by the following formula (3).

In the formula, R ⁶ represents an organic group having 1 to 8 carbon atoms substituted with a fluorine atom, and is not particularly limited as long as it is an organic group satisfying this condition, but is preferably a fluoroalkyl group such as methylene difluoride or trifluoromethyl, From the viewpoint of the solubility of the resulting polymer and the reliability of the device, it is particularly preferable that it is a trifluoromethyl group.

X ₁ and X ₂ in the formula (3) each independently represent a hydrogen atom, an organic group having 1 to 10 carbon atoms or a hydroxy group. Examples of the organic group having 1 to 10 carbon atoms include an alkyl group, a cycloalkyl group, an aromatic group, an allyl group, a benzyl group, a benzoyl group, a phenylamide group or a phenyl ester group. In view of the solubility and photosensitive properties of the resulting polymer, It is preferably a hydroxy group, and in particular, from the viewpoint of photosensitive properties, it is preferably a hydroxy group.

The component (A) (the polyimide precursor having the structural unit represented by the formula (1) or the polyimide obtained therefrom) is a component selected from a tetracarboxylic acid and a derivative thereof (hereinafter referred to as an acid component) and a diamine component And then dehydrating them by heating or chemically dehydrating them and imidizing them.

≪ Tetracarboxylic acid component >

The polyimide precursor having the structural unit represented by the formula (1) or the acid component used as the polyimide obtained therefrom is represented by the following formula (4). In addition, most of them are converted into the skeleton represented by the formula (2) by the reaction with the diamine component described later.

In the formula (4), R ⁷ represents an organic group having a sulfur atom. Any organic group may be used as long as it is a group having a sulfur atom, but it is preferably a sulfonyl group, a sulfide group or a sulfo group from the viewpoints of the solubility of the resulting polymer and the reliability of the device.

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'-diphenylsulfotetracarboxylic acid component compound, 3 , 3 ', 4,4'-diphenylsulfonyltetracarboxylic acid component compound and the like, but are not limited to these compounds.

If the molar ratio of the sulfur atom-containing acid component to the sulfur atom-free acid component is in the range of 40/60 to 99/1, the two acid component compounds may be used together for the copolymerization with the diamine component.

Examples of the acid component not containing a sulfur atom include compounds represented by the following formulas (5) to (8). Two or more kinds of these acid components may be used when copolymerizing. Particularly, from the viewpoint of reliability of the device, the molar ratio of the acid component having a sulfur atom to the acid component not containing a sulfur atom is preferably 50/50 to 80/20.

In formula (5), R ⁸ 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 ⁸ is, if the organic group satisfying the above conditions not particularly limited carbon organic group of atoms from 1 to 12 may be mentioned an alkyl group, fluoro alkyl group, a cycloalkyl group or an aromatic group such as a divalent organic group having an oxygen atom is An ether group or a siloxy group. Of these, a fluoroalkyl group or an ether group is preferable from the viewpoints of solubility and photosensitive properties, and in particular, fluoromethyl group is preferable from the viewpoint of solubility.

In the formula (6), m represents an integer of 0 or 1. Examples of the tetracarboxylic acid component satisfying these are pyromellitic acid and 1,2,6,7-naphthalenetetracarboxylic acid, but are not limited thereto.

In the formula (7), R ⁹ and R ¹⁰ represent an organic group having 1 to 12 carbon atoms. R ⁹ and R ¹⁰ may be any organic group, especially if they are organic groups having 1 to 12 carbon atoms. For example, an alkyl group, a fluoroalkyl group, a cycloalkyl group, or an aromatic group, but is not limited thereto.

In formula (8), R ¹¹ is a divalent organic group having 1 to 12 carbon atoms, and R ¹² and R ¹³ are organic groups having 1 to 12 carbon atoms. As the divalent organic group having 1 to 12 carbon atoms represented by R ¹¹ , a methylene group, an ether group, a trialkylsilyl group or a dialkyldisiloxane group can be exemplified, but these organic groups are not particularly limited. R ¹² and R ¹³ are not particularly limited as long as they are organic groups having 1 to 12 carbon atoms, and examples thereof include an alkyl group, a fluoroalkyl group, a cycloalkyl group, and an aromatic group.

Specific examples of the acid component not containing a sulfur atom represented by the formulas (5) to (8) include 2,2-bis (3,4-dicarboxyphenyl) hexafluoroisopropylene, Hexafluoroisopropylene 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 And aromatic tetracarboxylic acid components represented by the following general formula (1): 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 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-cyclopenta Acetic acid, bicyclo [2.2.2] octo-7-ene-2,3,5,6-tetracarboxylic acid, 2,3,4,5-tetrahydrofuran tetracarboxylic acid, 3,5,6-tri Carboxy-2-norobutanoic acid, and the like, but the present invention is not limited thereto.

Among the acid components not containing the sulfur atom, from the viewpoints of the solubility and photosensitive properties of the resulting polymer, particularly preferred are 2,2-bis (3,4-dicarboxyphenyl) hexafluoroisopropylene, 4,4'- It is preferable to use hexafluoroisopropylene diphthalic acid, pyromellitic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid and derivatives thereof, and in particular, from the viewpoint of solubility of the resulting polymer, 4,4'- It is preferable to use compounds such as fluoroisopropyidiopyridinediphthalic acid dianhydride and dihalide thereof.

≪ Diamine component >

The polyimide precursor having the structural unit represented by the formula (1) or the diamine component used as the polyimide obtained therefrom has a structure represented by the following formula (9).

R ⁶ in the formula (9) represents an organic group having 1 to 8 carbon atoms substituted with a fluorine atom, for example, a methylene difluoride, a trifluoromethyl group, or a fluorophenyl group. Is not particularly limited, but from the viewpoint of the solubility and photosensitive properties of the obtained polymer, it is preferably a trifluoromethyl group.

X ₃ and X ₄ in the formula (9) each independently represent a hydrogen atom, an organic group having 1 to 10 carbon atoms or a hydroxy group. Examples of the organic group having 1 to 10 carbon atoms include an alkyl group, a cycloalkyl group, an aromatic group, an allyl group, a benzyl group, a benzoyl group, a phenylamide group or a phenyl ester group. In view of the solubility and photosensitive properties of the resulting polymer, Or a hydroxy group, and in particular, from the viewpoint of photosensitive properties, it is preferably a hydroxy group.

Specific examples of the diamine component having an organic group substituted with a fluorine atom in the formula (9) include 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2- Bis (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-anilino) hexafluoropropane, 2,2- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, Bis (4-amino-4-hydroxyphenoxy) hexafluoropropane, 2,2-bis [4- Phenyl] hexafluoropropane, 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] hexafluoropropane, and the like. Further, in view of the solubility and photosensitive properties of the polymer to be obtained, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 2,2-bis ) Hexafluoropropane, and 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is particularly preferred in terms of the photosensitivity.

It is also possible to use diamine components that are soluble in a low-pollution organic solvent (component (C)), which will be described later, and do not contain a fluorine atom, for copolymerization. The other diamine component not containing a fluorine atom may be used in two or more types if at least one kind of diamine component having an organic group substituted with a fluorine atom is used.

Specific examples of the diamine component not containing a fluorine atom include p-phenylenediamine, m-phenylenediamine, 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'-diaminodi Phenyl 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 -Methylaniline), 4,4'-methylene-bis (2,6-diisopropylaniline), 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, benzidine, o- Tolylidine, 3,3 ', 5,5'-tetramethylbenzidine, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) ] Sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- 4-diaminophenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis ( Amino-4-hydroxyphenyl) ether, bis (4-amino-3-hydroxyphenyl) ether, bis Amino-3-hydroxyphenyl) methane, bis (4-amino-3-hydroxyphenyl) methane, bis (4-amino-3, 5-dihydroxyphenyl) sulfone, 4,4'-diamino-3,3'-dihydroxybis Phenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy- Dimethoxybiphenyl, 1,4-bis (3-amino-4-hydroxyphenoxy) benzene, 1,3- Amino-3-hydroxyphenoxy) benzene, 1,3-bis (4-amino-3-hydroxyphenoxy) Benzene, bis [4- (3-amino-4-hydroxyphenoxy) phenyl] sulfone, bis [4- 2,5-diamino benzoic acid, 3,5-diamino benzoic acid, 4,6-diamino-1,3-benzenedicarboxylic acid, 2,5-diamino- (4-amino-3-carboxyphenyl) ether, bis (4-amino-3,5-dicarboxyphenyl) ether, bis Dicarboxyphenyl) sulfone, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'- , 4'-diamino-3,3'-dicarboxy-5,5'-dimethoxybiphenyl, 1,4-bis (4-amino-3-carboxyphenoxy) benzene, Amino-3-carboxyphenoxy) benzene, bis [4- (4-amino- Cy) phenyl] sulfone or bis [4- (4-amino-3-carboxyphenoxy) phenyl] propane.

In order to improve the adhesion of the coating film formed by using the positive photosensitive resin composition containing the polyimide precursor having the structural unit represented by the formula (1) or the polyimide obtained therefrom to the substrate, Siloxane compounds may be used in combination. As such a siloxane-containing diamine, bis (3-aminoalkyl) -1,1,3,3-tetramethyldisiloxane is preferable, and from the viewpoints of adhesiveness to a substrate and solubility, bis (3-aminopropyl) , And 3,3-tetramethyldisiloxane are more preferable.

The siloxane-containing diamine is preferably used in a molar ratio of 1 to 30% of the total amount of the diamine component from the viewpoint of adhesiveness to the substrate and developability. If it exceeds 30 mol%, the developability is lowered and the residue tends to remain on the substrate. , More preferably 1 to 20 mol%, and further preferably 1 to 10 mol%.

≪ Component (B) >

The photoacid generator which is the component (B) is not particularly limited as long as it has a function of directly or indirectly generating an acid by irradiation of light used for exposure and increasing the solubility of the irradiated portion in an alkaline developer It does not. The photoacid generators may be used alone or in combination of two or more.

As the photoacid generator that is the component (B), any of conventionally known photoacid generators may be used. Specific examples thereof include o-quinonediazide compounds, allyldiazonium salts, diallyl iodonium salts, triallyl sulfonium salts, o- Nitrobenzyl esters, p-nitrobenzyl esters, trihalomethyl-substituted s-triazine derivatives, and imidosulfonate derivatives.

If necessary, a sensitizer may be used together with the photoacid generator which is the component (B). Examples of the sensitizer include perylene, anthracene, thioxanthone, microcrystalline, benzophenone, and fluorene, but are not limited thereto.

Among the photoacid generators as the component (B), the o-quinonediazide compound is preferable because it can obtain high sensitivity and high resolution in the coating film obtained by using the positive photosensitive resin composition.

The o-quinonediazide compound is usually prepared by condensation reaction of a compound having o-quinonediazide sulfonyl chloride and at least one group selected from a hydroxyl group and an amino group in the presence of a basic catalyst to obtain an o-quinonediazide sulfonic acid ester or o- Quinonediazide sulfonamide. ≪ / RTI >

Examples of the o-quinonediazidesulfonic acid component constituting the above-mentioned o-quinonediazide sulfonyl chloride include 1,2-naphthoquinone-2-diazide-4-sulfonic acid, 1,2-naphthoquinone- 2-diazide-5-sulfonic acid, and 1,2-naphthoquinone-2-diazide-6-sulfonic acid.

Specific examples of the compound having a hydroxy group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, o-methoxyphenol, 4,4-isopropylpyridinediphenol, , 1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxyphenylsulfone, 4,4-hexafluoroisopropylidene diphenol, 4,4 ' Tris (4-hydroxyphenyl) ethane, 4,4 '- [1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethyl Lidene] bisphenol, methyl 3,4,5-trihydroxybenzoate, propyl 3,4,5-trihydroxybenzoate, 3,4,5-trihydroxybenzoic acid isoamyl ester, 3,4,5-tri 2-ethylbutyl ester of hydroxybenzoic acid, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2, Phenol compounds such as 3,4,4'-tetrahydroxybenzophenone and 2,3,4,2 ', 4'-pentahydroxybenzophenone, ethers such as ethanol, 2-propanol, 4- Butanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, Of aliphatic alcohols.

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

Specific examples of the compound having both a hydroxyl group and an amino group include o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2,3-diaminophenol, , 4,4'-diamino-4''-hydroxytriphenylmethane, 4-amino-4 ', 4'-dihydroxytriphenylmethane, bis (4-amino-3-carboxy- (4-amino-3-carboxy-5-hydroxyphenyl) sulfone, 2,2-bis (4-amino-3-carboxy-5-hydroxyphenyl) hexafluoropropane, 2-aminoethanol, 3-amino Propanol, 4-aminocyclohexanol, and other alkanol amines.

quinonediazide sulfonyl chloride and a compound having at least one selected from a hydroxyl group and an amino group, the hydroxy group or a part or all of the hydroxyl group or the amino group of the compound is reacted with o-quinonediazide sulfonyl chloride o-quinonediazide sulfonyl chloride An o-quinonediazide compound of a divalent substituent, a trivalent substituent, a quadruple substituent, or a pentavalent substituent substituted with a fluorine-containing group can be obtained. When the o-quinone diazide compound is used as a component of the positive photosensitive resin composition, the above-mentioned o-quinonediazide compound having a multiple substituent may be used alone or in combination with two or more of the above- It is generally used as a mixture.

Among the o-quinonediazide compounds described above, in the coating film obtained by using the positive photosensitive resin composition, development residuals (residues of the pattern edge portions) of the pattern bottom at the time of development are well balanced in the difference in development solubility between the exposed portion and the unexposed portion, Quinone diazidesulfonic acid ester of p-cresol, 4,4'- [1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol quinonediazidesulfonic acid ester of methyl 3,4,5-trihydroxybenzoate, o-quinonediazidesulfonic acid ester of 2,3,4-trihydroxybenzophenone, or o- , And o-quinonediazidesulfonic acid esters of 3,4,4'-tetrahydroxybenzophenone. These compounds may be used alone or in admixture of two or more selected arbitrarily from these compounds .

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

≪ Component (C) >

The solvent (C) used in the positive photosensitive resin composition of the present invention is preferably a solvent having a high solubility in the component (A) (the polyimide precursor having the structural unit represented by the formula (1) or the polyimide obtained therefrom) (B) component (photoacid generator) and other components to be described later, and ease of handling in the positive-working photosensitive resin composition. In view of being a low-pollution organic solvent, an alcohol or alkyl having 4 or more carbon atoms Ester is preferred. As typical solvents, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether,? -Butyrolactone, ethyl lactate and butyl lactate, n-butanol, sec- methylcellosolve acetate, ethyl cellosolve acetate, butyl carbitol, butyl carbitol acetate, ethyl carbitol, ethyl carbitol acetate, ethylene glycol monomethyl ether acetate, Monopropyl ether, ethylene glycol monobutyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, Dipropylene glycol monoacetate monopropyl ether, 2-ethoxyethanol, 2-butoxy But are not limited to, ethanol, methyl lactate, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate or butyl butyrate. These solvents may be two or more kinds of mixed solvents.

Particularly, from the viewpoint of easiness of handling in the positive photosensitive resin composition, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether,? -Butyrolactone, ethyl lactate and lactic acid Butyl, or mixtures of two or more thereof.

In addition to the above-mentioned solvents, other solvents such as acetone, methanol, ethanol, isopropyl alcohol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isobutyl 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, But are not limited to, ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, N, N-dimethylacetamide, N-hexane, n-pentane, n-octane, 2-methoxyethanol, di-n-propyl alcohol, Ethyl ether, cyclohexanone, 3- When propionic acid, may be used by mixing a solvent such as 3-methoxy propionic acid or diglyme. However, from the viewpoint that these other solvents are used in the conventional positive photosensitive resin composition (not the low-emission organic solvent), the smaller the amount of these solvents, the better.

≪ Component (D) >

The positive photosensitive resin composition of the present invention may contain a maleimide compound as the component (D). The maleimide compound as the component (D) is not particularly limited as long as it is a compound soluble in an alkali developing solution in a developing process of a coating film obtained using the positive photosensitive resin composition of the present invention. As the maleimide compound as the component (D), the structure 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.

The maleimide compound having a structure in which the maleimide moiety mentioned above is directly connected to the aromatic ring and hydrogen atoms are directly connected to the adjacent aromatic carbon may be a compound represented by the following formula (10).

In the formula (10), R ¹⁴ represents a divalent organic ^{group, R 15, R 16, R} 17, R 18, R 19, R 20, R 21, R 22, R 23 and R ²⁴ is to independently hydrogen Atom and an organic group having 1 to 12 carbon atoms.

Among them, it is preferable to use, as the component (D), a maleimide compound having a structure in which R ¹⁴ is represented by the following formula (11) in the above formula (10).

In the formula (11), l and k each independently represent 0 or 1, and each of X ₅ , X ₆ and X ₇ independently represents an organic group having 1 to 12 carbon atoms, an oxygen atom, a sulfur atom, Represents a divalent organic group.

Particularly, in the formula (11), l and k are 1, X ₅ and X ₇ are oxygen atoms, and X ₆ is a dimethylmethyl group.

Specific examples of the maleimide compound represented by the formula (10) as the component (D) include 2,2-bis (3-amino-4-maleimide) hexafluoropropane, 4,4'-dimaleimidodiphenyl Ether, 3,4'-dimaleimide diphenyl ether, 3,3'-dimaleimide diphenyl ether, 4,4'-dimaleimide diphenyl sulfide, 4,4'-dimaleimide diphenyl methane , 3,4'-dimaleimide diphenylmethane, 3,3'-dimaleimide diphenylmethane, 4,4-methylene-bis (2-methylmaleimide), 4,4'-dimaleimide diphenyl Sulfone, 3,3'-dimaleimidodiphenylsulfone, 1,4'-bis (4-maleimidophenoxy) benzene, 1,3'-bis (4-maleimidophenoxy) Bis [4- (3-maleimidophenoxy) phenyl] sulfone, bis [3- (4-maleimidophenoxy) (4-maleimidophenoxy) phenyl] sulfone, bis [3- (3-maleimidophenoxy) phenyl] sulfone, 2,2'- -ratio And [4- (3-aminophenoxy) phenyl] propane, but are not limited thereto.

Among these compounds, 4,4'-dimaleimidodiphenylmethane and 2,2'-bis [4- (4-maleimidophenoxy) phenyl] propane are preferable from the standpoint of easiness of availability, Is more preferably 2,2'-bis [4- (4-maleimidophenoxy) phenyl] propane.

The maleimide compound (D) in the present invention can be used in combination of two or more kinds.

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

≪ Component (E) >

The positive photosensitive resin composition of the present invention may contain a crosslinkable compound as the component (E). The crosslinkable compound as the component (E) is a polyimide precursor which is a component (A) or a polyimide precursor (B) which is a component (A) in the step of converting a coating film obtained by using the positive photosensitive resin composition of the present invention into a cured film Is not particularly limited as far as it is a compound having a group capable of reacting with an organic group contained in at least one of the photoacid generators.

Examples of the crosslinkable compound as the component (E) include compounds containing two or more epoxy groups, melamine derivatives in which the hydrogen atom of the amino group has a methylol group, an alkoxymethyl group, or a group substituted with both of them, a benzoguanamine derivative, And the like. The melamine derivative and the benzoguanamine derivative may be a dimer or a trimer, or may be a mixture selected arbitrarily from a monomer, a dimer and a trimer. The melamine derivative and the benzoguanamine derivative preferably have an average of 3 or more and less than 6 methylol groups or alkoxymethyl groups per triazine ring.

In the present invention, the crosslinkable compound (E) may be used in combination of two or more kinds.

As the crosslinkable compound as the component (E), it is preferable to use a commercially available compound in view of availability. Specific examples (trade names) are shown below, but the present invention is not limited thereto.

Examples of compounds containing two or more epoxy groups include EPOLED GT-401, EPOLED GT-403, EPOLED GT-301, EPOLED GT-302, SOROCIDE 2021 and SOROCIDE 3000 Epikote 1001, Epikote 1002, Epikote 1003, Epikote 1004, Epikote 1007, Epikote 1009, Epikote 1010, Epikote 828 (or more) having a cyclohexene structure such as Epikote (Manufactured by Japan Epoxy Resin Co., Ltd.), bisphenol F type epoxy compounds such as Epikote 807 (manufactured by Japan Epoxy Resin Co., Ltd.), Epikote 152, Epikote 154 (above, Japan Epoxy Resin Co., ECON-102S, ECON-103S, ECON-104S, ECON-1020, ECON-1025 and ECON-1025 compounds such as EPPN201 and EPPN202 (manufactured by Nippon Kayaku Co., Cresol novolak type epoxy compounds such as Epikote 180-S (available from Nippon Kayaku Co., Ltd.) and Epikote 180S75 (manufactured by Japan Epoxy Resin Co., Ltd.), Denacol EX-252 Araldite CY-184 (manufactured by CIBA-GEIGY AG), Epiclon 200, Epiklon 400 (manufactured by Ciba-Geigy AG), CY175, CY177, CY179, Araldite CY-182, Araldite CY- ED-5661 and ED-5662 (all manufactured by Celanese Coatings Co., Ltd.), Epikote 871 and Epikote 872 (all manufactured by Japan Epoxy Resin Co., Ltd.) (manufactured by Dainippon Ink and Chemicals, Inc.) Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-411, Denacol EX-512, Denacol EX-522 And aliphatic polyglycidyl ether compounds such as Denacol EX-421, Denacol EX-313, Denacol EX-314 and Denacol EX-312 (manufactured by Nagase ChemteX Corporation).

A melamine derivative in which the hydrogen atom of the amino group has a methylol group, an alkoxymethyl group or a group substituted on both of them, a benzoguanamine derivative or a glycoluril include MX-750 in which methoxymethyl groups are substituted in an average of 3.7 per triazine ring, triazine ring 1 MW-30 (manufactured by Sanwa Chemical Industry Co., Ltd.) having an average of 5.8 substituents of methoxymethyl groups per unit, or Cymel 300, Cymel 301, Cymel 303, Cymel 350, Cymel 370, Cymel 771, Cymel 325 , Methoxymethylated melamine such as Cymel 327, Cymel 703, Cymel 712, Cymel 235, Cymel 236, Cymel 238, Cymel 212, Cymel 253 and Cymel 254. Butoxymethylated melamines such as melamine, Cymel 506 and Cymel 508, methoxymethylated isobutoxymethylated melamine containing carboxyl groups such as Cymel 1141, methoxymethylated ethoxymethylated benzoguanamines such as Cymel 1123, Cymel 1123- Methoxymethylated < / RTI > Butoxymethylated benzoguanamine such as Cymel 1128, and a carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80 (manufactured by Nippon Saiketsu Industries Co., Ltd.) Mitsui Cyanamid), butoxymethylated glycoluril such as Cymel 1170, methylol glycoluril such as Cymel 1172, and the like.

The content of the crosslinkable compound as the component (E) in the positive photosensitive resin composition of the present invention is not particularly limited, but from the viewpoints of storage stability of the positive photosensitive resin composition, low absorbability of the resulting cured film, and heat resistance and chemical resistance It is preferably 5 to 100 parts by mass based on 100 parts by mass of the polyimide precursor which is the component A), and is preferably 5 to 20 parts by mass from the viewpoint of storage stability.

<Other additives>

In addition, the positive photosensitive resin composition of the present invention may contain additives such as a surfactant, a rheology modifier, and a silane coupling agent, a pigment, a dye, a storage stabilizer, a defoaming agent, or a polyhydric phenol , A dissolution accelerator such as a polyglycolic acid, and the like.

Examples of the surfactant that can be used for the purpose of improving the applicability of the positive photosensitive resin composition of the present invention include a fluorine surfactant, a silicone surfactant, and a nonionic surfactant. As this type of surfactant, commercially available products such as those available from Sumitomo 3M Ltd., Dainippon Ink & Chemicals Incorporated, or Asahi Glass Co., Ltd. can be used. These commercial products are good because they are readily available. As specific examples thereof, there may be mentioned Fafto EF301, EF303, EF352 (made by Muko Corporation), Mecafax F171 and F173 (manufactured by Dainippon Ink and Chemicals, Inc.), Florado FC430 and FC431 (manufactured by Sumitomo 3M Co., Surfactants such as Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105 and SC106 (manufactured by Asahi Glass Co., Ltd.).

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

When a surfactant is used, its content is usually 0.2 mass% or less, preferably 0.1 mass% or less, in 100 mass% of the positive photosensitive resin composition. Even if the amount of the surfactant used is set to an amount exceeding 0.2 mass%, the effect of improving the coating property becomes dull and not economical.

&Lt; Positive photosensitive resin composition >

The positive photosensitive resin composition of the present invention comprises a polyimide precursor as the component (A) or a polyimide obtained therefrom, a photoacid generator as the component (B), and a solvent (C) A crosslinking compound as a component (E), and other additives such as a surfactant.

Among these, preferable examples of the positive photosensitive resin composition of the present invention are as follows.

[1] A positive photosensitive resin composition comprising 0.01 to 100 parts by mass of a component (B) based on 100 parts by mass of the component (A), wherein the components are dissolved in a solvent (C).

[2] A positive photosensitive resin composition comprising, in addition to the composition of [1], a component (D) in an amount of 5 to 100 parts by mass based on 100 parts by mass of the component (A).

[3] The positive photosensitive resin composition according to the above [2], wherein the component (E) is contained in an amount of 5 to 100 parts by mass based on 100 parts by mass of the component (A).

The solid content ratio in the positive photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in a solvent, but it is generally in the range of solid content concentration of 1 to 50 mass% It is possible to easily form a coating film by preparing a solution of the resin composition. Here, the solid content means that the solvent (C) is excluded from all components of the positive photosensitive resin composition.

The method of preparing the positive photosensitive resin composition of the present invention is not particularly limited. Since this kind of composition is usually used in the form of a solution, the positive photosensitive resin composition of the present invention generally contains the components (A), (B) and optionally (D) ) Solvent to give a homogeneous solution, or a method in which other additives are added and mixed at a proper stage of the preparation method.

In the preparation of the positive photosensitive resin composition of the present invention, the reaction solution obtained by polymerizing the component (A), that is, the component selected from the tetracarboxylic acid and the derivative thereof, and the diamine component in an organic solvent, It is possible. As the organic solvent to be used at this time, a solvent described in the above-mentioned (C) solvent may be mentioned. In this case, when a homogeneous solution is prepared by adding the component (B) or the like to the reaction solution of the component (A) in the same manner as described above, a further solvent (C) may be further added for the purpose of adjusting the concentration, , And the organic solvent used for preparing the component (A) and the solvent (C) used for adjusting the concentration may be the same or different.

When plural kinds of organic solvents are used, a plurality of types of organic solvents may be mixed at first, and a plurality of kinds of organic solvents may be added in a divided manner.

The prepared solution of the positive photosensitive resin composition is preferably filtered after using a filter having a diameter of about 0.2 탆 or the like.

&Lt; Coating film and cured film &

In general, the positive photosensitive resin composition of the present invention is coated on a substrate having 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, It is possible to form a coating film composed of the positive photosensitive resin composition of the present invention by pre-drying at a temperature of 60 캜 to 160 캜, preferably 70 캜 to 130 캜.

After the coating film is formed, the coating film is exposed using a mask having a predetermined pattern, for example, with ultraviolet rays, and developed with an alkaline developer to clean and remove the exposed portion, thereby forming a relief pattern having a sharp cross section.

The alkaline developer used herein is not particularly limited as long as it is an alkaline aqueous solution, and examples thereof include aqueous solutions of alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate, hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, An aqueous solution of quaternary ammonium, and an aqueous amine solution of ethanolamine, propylamine, ethylenediamine and the like.

The concentration of the alkaline developing solution is generally 10% by mass or less, and industrially, an alkaline aqueous solution of 0.1 to 3.0% by mass is used. In addition, the alkaline developer may contain an alcohol or a surfactant, and preferably contains about 0.05 to 10% by mass each.

In the developing step, the temperature of the alkaline developing solution can be arbitrarily selected. However, when the positive photosensitive resin composition of the present invention is used, since the solubility of the exposed portion is high, development with an alkaline developer can be easily performed at room temperature.

The resulting substrate having a relief pattern is subjected to heat treatment (firing) at a temperature of 180 to 400 占 폚 to obtain a cured film having a low absorbability and having a relief pattern having excellent electrical properties and good heat resistance and chemical resistance.

The cured film obtained from the positive photosensitive resin composition of the present invention has such excellent effects and can be used in electric / electronic devices, semiconductor devices, display devices and the like. Particularly, since the cured film obtained from the positive photosensitive resin composition of the present invention has the characteristic effect that the reliability of the organic EL element (a kind of LED (Light-Emitting Diode) element) is high, the organic EL element Ion migration of the copper wiring to the insulating film, the barrier rib material, or the semiconductor package is very useful in a buffer code which is greatly influenced by the absorbency of the insulating film.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example

[Abbreviations used in Examples]

The meanings of abbreviations used in the following embodiments are as follows.

&Lt; Diamine component >

BAHF: 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane

BATF: 2,2'-bis (3-amino-4-tolyl) hexafluoropropane

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

&Lt; Tetracarboxylic acid component >

6FDA: 4,4'-hexafluoroisopropylidene diphthalic anhydride

DSDA: 3,3'-4,4'-diphenylsulfone tetracarboxylic anhydride

PMDA: pyromellitic anhydride

ODPA: 3,3 ', 4,4'-diphenyl ether tetracarboxylic anhydride

<Solvent>

PGMEA: Propylene glycol monomethyl ether acetate

PGME: Propylene glycol monomethyl ether

NMP: N-methylpyrrolidone

? -BL:? -butyrolactone

&Lt;

P200: P-200 (trade name) manufactured by Toyobo Chemical Co., Ltd. 4,4 '- [1- [4- [1- (4-hydroxyphenyl) -1- methylethyl] phenyl] ethylidene] bisphenol 1 mole And 2 moles of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride,

<Component of maleimide>

BMI-80: 2,2'-bis [4- (4-maleimidophenoxy) phenyl] propane

[Measurement of number-average molecular weight and weight-average molecular weight]

The weight average molecular weight (hereinafter referred to as Mw) and the molecular weight distribution of the polymer were measured using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF805L) manufactured by Nihon Bunko Co., (Column temperature: 50 占 폚) at a flow rate of 1 ml / min and eluted. Mw is expressed in terms of polystyrene.

[Measurement of imidization rate]

The imidization ratio was calculated from the proton ratio of the aromatic proton ratio of the polymer skeleton and the NH moiety of the polyamic acid by 1 H-NMR measurement using an NMR apparatus (JNM-LA series, manufactured by Nihon Denshi Co., Ltd.).

[Synthesis Example]

&Lt; Preparation of polyamic acid solution (Synthesis Example 1) >

(0.199 mol) of BAHF, 5.51 g (0.0022 mol) of APDS and 71.5 g (0.199 mol) of DSDA were dissolved in 850 g of PGME to a concentration of 15 wt%, followed by reaction at 60 DEG C for 24 hours. The polymer thus obtained had Mw of 8600 and a molecular weight distribution of 1.55. 1.00 g of the resulting polymer solution was placed in an aluminum cup and heated on a hot plate for 2 hours to calculate the solid content. The solid content concentration of the solid obtained was 16.39 wt%. The polymer was further precipitated in a 50 wt% methanol aqueous solution (8000 times) of the polymer solution (4000 g) and dried under reduced pressure to obtain a polyamic acid powder. The yield of the obtained polymer was 91% and the imidization rate was 62%. The obtained polymer was soluble in PGME and PGMEA.

&Lt; Preparation of various polyamic acid solutions (Synthesis Examples 2 to 5) >

Various diamines and acid dianhydrides were dissolved in PGME so as to have a concentration of 15 wt%, and a polymer was synthesized by the same method as in Synthesis Example 1. Table 1 shows diamine, acid dianhydride, amount of solvent used, Mw and molecular weight distribution of the obtained polymer, solid concentration of the obtained polymer solution, and imidization ratio. These polymers were also soluble in PGMEA.

&Lt; Preparation of polyamic acid solution (Synthesis Example 6) >

NMP anhydride in which various diamines were dissolved was added and reacted for 4 hours to synthesize a polymer. Thereafter, 50 g of the reaction solution was poured into 1000 ml of pure water, the precipitate was filtered, and then dried under reduced pressure to obtain a polyamic acid. The amounts of diamine, acid dianhydride, solvent used, Mw and molecular weight distribution of the obtained polymer, solid concentration and imidization rate were shown in Table 1. Since the resulting polymer was insoluble in either PGME or PGMEA, the reaction solution was used as it was for the preparation of the following positive photosensitive resin composition.

As in Synthesis Example 1, a polymer was synthesized in PGME in which various diamines were dissolved. As a result, the polymer was precipitated at 1 hour after the reaction.

Polymer composition Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 Polyamide acid (partially imidized) P1 P2 HP1 HP2 HP3 HP4 Diamine component




BAHF (g) 26.6 58.4 59.8 BATF (g) 68.0 DDM (g) 7.11 6.07 21.6 APDS (g) 5.51 1.00 2.53 3.89 2.46 DBA (g) 16.7 12.0 TFMB (g) 79.8 Tetracarboxylic acid component


6FDA (g) 62.0 77.1 DSDA (g) 71.5 34.1 PMDA (g) 4.46 61.4 38.9 ODPA (g) 70.2 Solvent ^{* 1}
PGME (g) 850 850 850 850 850 NMP (g) 425 Weight average molecular weight (Mw) 8600 8400 12500 7900 8500 9040 Molecular weight distribution 1.55 1.93 1.96 1.46 1.66 1.88 Solid content concentration ^{* 2} (mass%) 16.39 15.81 15.52 15.91 15.52 15.00 ^{* 2} Imidization rate (%) 62 78 45 43 75 9

* 1: Solvent used for preparation * 2: Solid content concentration of reaction solution

[Production of positive-type photosensitive resin composition: Examples 1 to 3, Comparative Examples 1 to 4]

(A), the component (B), the solvent (C), the component (D) and the fluorine-containing surfactant (manufactured by Dainippon Ink and Chemicals, Inc. under the trade name of Mekafax R-30 ) Were mixed in a predetermined ratio and stirred at room temperature for 3 hours or more to prepare a homogeneous solution, whereby positive-working photosensitive resin compositions of each of Examples and Comparative Examples were prepared.

Composition of positive photosensitive resin composition No. (A) Component (g) (B) Component (g) (C) Component (g) (D) Component (g) Surfactant (g) Example 1 P1
3.0 P200
0.246 PGME
1.07 R-30
0.0002 Example 2 P2
3.0 P200
0.238 PGME
0.92 R-30
0.0002 Example 3 P1
3.0 P200
0.246 PGME / 1.07
γ-BL / 1.26 BMI-80
0.246 R-30
0.0002 Comparative Example 1 HP1
3.0 P200
0.233 PGME
1.411 R-30
0.0002 Comparative Example 2 HP2
3.0 P200
0.143 PGME
0.487 R-30
0.0002 Comparative Example 3 HP3
3.0 P200
0.140 PGME
0.401 R-30
0.0002 Comparative Example 4 HP4
3.0 P200
0.135 NMP
0.287 R-30
0.0002

[Evaluation of Photosensitive Property: Examples 1 to 3, Comparative Examples 1 to 4]

Photosensitive properties of each of the obtained positive photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 4 were evaluated by the following methods. The obtained results are shown in Table 3.

<1. Thickness before heat treatment (baking)>

The positive photosensitive resin composition was coated on a 25 mm.times.25 mm stepped ITO substrate (manufactured by Sanyo Shinkuko Kogyo Co., Ltd.) using a spin coat, and then prebaked on a hot plate at a temperature of 100.degree. C. for 120 seconds to form a coating film. The film thickness was measured using a contact type film thickness meter (Dektak 3ST manufactured by ULVAC Co., Ltd.).

<2. After development, the film thickness, resolution (line width) >

The obtained coating film was irradiated with infrared light for 70 seconds (70 mJ / cm ² ) using an ultraviolet irradiator PLA-501 manufactured by Canon Inc. through a line / space mask of 100 m / 200 m. After exposure, the substrate was immersed in a tetramethylammonium hydroxide aqueous solution (concentration of the aqueous solution used in each Example was set forth in Table 3) at 23 占 폚 for 30 seconds to carry out development, and the film thickness after development was measured.

Further, the coated film after development was observed with an optical microscope to determine the minimum line width at which lines / spaces were formed without pattern separation as the resolution.

<3. Thickness after heat treatment (baking) >

&Lt; 1. > The photosensitive resin coating film formed on the stepwise ITO substrate was heated on a hot plate at 100 DEG C for 120 seconds. Next, after the film was heated at 230 DEG C for 30 minutes without exposure, the film thickness was measured.

Evaluation results of photosensitivity NO. Film thickness before heat treatment (占 퐉) Developer concentration
(23 占 폚, mass%) Film thickness after development (占 퐉) Resolution (탆) After heat treatment,
(Μm) Example 1 0.9 0.8 0.9 3 0.8 Example 2 1.0 0.8 1.0 3 0.9 Example 3 1.2 2.4 1.1 3 1.0 Comparative Example 1 0.9 2.4 1.0 5 0.9 Comparative Example 2 1.1 0.4 1.0 3 1.0 Comparative Example 3 1.0 0.2 1.0 10 0.9 Comparative Example 4 2.2 - - - 1.9

4. Evaluation of device characteristics: Examples 1 to 3 and Comparative Examples 1 to 4 [

The polyimide pattern obtained in < 2. > (in Comparative Example 4, the pattern was completely dissolved after development, a polyimide film was thus obtained on the stepwise ITO substrate without being developed and then developed) was placed in a UV ozone cleaning apparatus ND-1032 (manufactured by Nissan Kagakuko Kogyo Co., Ltd.) was applied by spin coating and heat-treated (fired) at 200 캜 for 1 hour on a hot plate to obtain a film having a thickness of 30 nm. Then in the middle 15mm ² The device was cut by leaving a quadrangle and under vacuum conditions, device elements were deposited in the order of alpha -NPD, Alq3, FLi and Al in this order. The deposition component was measured with a crystal oscillation type film forming controller CRTM-6000 (manufactured by Nippon Shin Kogyutsu Co., Ltd.). Thereafter, a current of 9 V was passed through the device, and the light emitting surface was observed with an optical microscope. The device components, the deposition amount, and the results of observation and evaluation of the light emitting surface are shown in Table 4.

Evaluation results of device characteristics Yes Polyimide alpha -NPD (nm) Alq3 (nm) FLi (nm) Al (nm) Evaluation of light emitting surface * Example 1 P1 35 50 0.5 100 ◎ Example 2 P2 35 50 0.5 100 ◎ Example 3 P1 35 50 1.5 100 ◎ Comparative Example 1 HP1 35 50 0.5 100 X Comparative Example 2 HP2 35 50 0.5 100 X Comparative Example 3 HP3 35 50 0.5 100 X Comparative Example 4 HP4 35 50 0.5 100 X

* Evaluation of light emitting surface: Bright emission can be seen from the edge portion.

                ○: There is blurring in a part of the interface between the edge portion and the light emitting surface.

                ?: There is blurring in the entire interface between the edge portion and the light emitting surface.

X: Shadows exist at the interface between the edge portion and the light emitting surface.

[Device evaluation result]

In the device using P1 or P2, the polyimide pattern edge portion also showed clear luminescence. This indicates that the partition wall elements using the polyimides of Examples 1 to 3 can manufacture pixels without adversely affecting the light emitting surface.

On the other hand, in the device using HP1 to HP4, since shadows exist on the interface between the polyimide pattern edge portion and the light emitting surface to cause a defective light emission, when the polyimide of Comparative Examples 1 to 4 is used as an element, It was a result of concern.

[Industrial applicability]

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, It is possible to form a fine pattern without reducing the film thickness of the light portion. In addition, the organic EL device using the film cured after the pattern formation exhibits a clear luminous surface without shadows.

Claims (10)

(A) a polyimide precursor or a polyimide obtained therefrom, and (B) an o-quinone diazide compound which is a compound which generates an acid by light as a component (B) As the photosensitive resin composition,
The component (A) is a polyimide precursor obtained by polymerizing a tetracarboxylic acid component and a diamine component, or a polyimide obtained therefrom,
Wherein the tetracarboxylic acid component comprises a compound represented by the following formula (4)

(Wherein R ⁷ represents a sulfonyl group, a sulfide group or a sulfo group).
The diamine component may be a diamine compound represented by the following formula (9)

(Wherein R ⁶ represents an organic group having 1 to 8 carbon atoms substituted with a fluorine atom, and X ₃ and X ₄ each independently represent a hydrogen atom, an organic group having 1 to 10 carbon atoms or a hydroxy group.)
A diaminosiloxane compound,
Wherein the positive photosensitive resin composition further comprises a maleimide compound represented by the following formula (10) as a component (D) in an amount of 5 to 100 parts by mass based on 100 parts by mass of the component (A).

(Wherein R ¹⁴ represents a divalent organic group represented by the following formula (11) and R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ Each independently represent a hydrogen atom or an organic group having 1 to 12 carbon atoms.

(Wherein l and k are 1, X ₅ and X ₇ are an oxygen atom, and X ₆ represents a dimethylmethyl group.)
The method according to claim 1,
Wherein the diaminosiloxane compound is bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane.
The method according to claim 1,
Wherein the tetracarboxylic acid component is a tetracarboxylic acid component further comprising a compound represented by the formula (4) and represented by the following formula (5).

(Wherein R ⁸ represents a divalent fluoroalkyl group having 1 to 12 carbon atoms)
The method according to claim 1,
Wherein the component (B) is a naphthoquinone diazidesulfonic acid ester compound.
The method according to claim 1,
Wherein the (C) solvent is at least one selected from the group consisting of alcohols having 4 or more carbon atoms and alkyl esters.
The method according to claim 1,
, And 0.01 to 100 parts by mass of the component (B) based on 100 parts by mass of the component (A).
A cured film obtained by using the positive photosensitive resin composition according to any one of claims 1 to 6.
An electronic part having the cured film according to claim 7.
An organic EL device having the cured film according to claim 7.
A positive photosensitive resin composition according to any one of claims 1 to 6, which is applied onto a substrate, heated and dried, and irradiated with ultraviolet light to develop the relief pattern.