KR20100016021A - Positive photosensitive resin composition, cured film thereof, and display element - Google Patents

Abstract

Disclosed is a positive photosensitive resin composition as a material for a display element which enables a sharp image display in a display device such as an organic EL device. This positive photosensitive resin composition is soluble in a low-pollution organic solvent. Specifically disclosed is a positive photosensitive resin composition containing a polyimide precursor having a structural unit represented by the formula (1) below or a polyimide obtained therefrom as a component (A), and a compound which generates an acid when irradiated with light as a component (B). The components (A) and (B) are dissolved in a solvent (C). (1) (In the formula (1), Rrepresents an aromatic group represented by the following formula (2): (2) (wherein Rrepresents an organic group having a sulfur atom, and Rand Rindependently represent a hydrogen atom or an organic group having 1-20 carbon atoms); Rrepresents an aromatic group having a fluorine atom; and n represents a natural number.)

Description

Positive photosensitive resin composition, cured film and display element thereof Positive photosensitive resin composition, Cured Film Thereof, and Display Element

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to photosensitive materials suitable for surface protection films, interlayer insulation films, passivation films, electrode protection layers and the like for electric and electronic devices, in particular, semiconductor devices and display devices. In more detail, when the obtained cured film soluble in a low pollution organic solvent is used as an insulating film of an organic EL device device, an excellent positive photosensitive resin composition, a cured film thereof, and various kinds of the cured film using the cured film, which do not cause poor light emission on the light emitting surface It is about material.

Photosensitive insulating films made of photosensitive resins typified by photosensitive polyimide resins having excellent mechanical properties and high heat resistance have been widely used in the semiconductor and display fields. In particular, when the photosensitive insulating film is used as a protective film such as a thin film transistor (TFT) protective film of a liquid crystal display device or an electrode protective film of an organic EL device or the like, the above-described functions as well as the reliability improvement of the insulating film are required. In addition, characteristics such as simplification of the device process, good shape of the protective film, and in addition to being soluble in a biodegradable solvent in terms of productivity are required. In particular, in the above-described apparatus, since it is an important condition not to cause display defects, there is a demand for not causing device defects caused by moisture or photosensitizer in the cured film entering the final product.

As a positive photosensitive resin composition which has been proposed so far, there is a polyimide-based positive photosensitive resin composition in which the acidity of the polyamic acid is reduced by using a basic organic compound such as triethylamine to suppress the dissolution rate into the alkaline developer ( Patent document 1). Moreover, positive type photosensitive resin composition (patent document 2) which consists of a polyimide resin and a quinone diazide compound containing a phenolic hydroxyl group and a nonphenolic hydroxyl group for the purpose of improving the residual film retention rate and mechanical strength after thermosetting, A resin composition containing a phenolic compound in addition to a polyamide and a diazoquinone compound, which is a precursor of polyimide, has been proposed for the purpose of high residual film ratio and improved adhesion to a sealing resin (Patent Document 3). The materials proposed in these documents are described as having high sensitivity and excellent mechanical properties, but there is concern about damage to the device emitting surface due to the permeation of additives (such as triethylamine or phenolic compounds) in the final cured film. As described above, in the conventional positive photosensitive polyimide resin composition, it is difficult to provide a material that satisfies the luminescence property as a partition of the light emitting element.

<Patent Document 1> US Patent No. 4880722

<Patent Document 2> Japanese Patent Application Laid-Open No. 2004-94118

<Patent Document 3> Publication No. 9-302221

This invention is made | formed in view of the said situation, and is providing the positive photosensitive resin composition used as a display element material which can display a clear image in display apparatuses, such as an organic EL device. Another object of the present invention is to provide a positive photosensitive resin composition dissolved in a low pollution organic solvent.

MEANS TO SOLVE THE PROBLEM This inventor discovered this invention as a result of earnestly researching in order to solve the said subject.

That is, the polyimide precursor which has a structural unit represented by following formula (1) as (A) component as a 1st viewpoint, or the polyimide obtained from these, and the compound which generate | occur | produces an acid by light in (B) component are contained, Positive photosensitive resin composition in which these were melt | dissolved in (C) solvent.

(In Formula (1), R ¹ is Formula (2).

(In formula (2), R <^3> represents the organic group which has a sulfur atom, R <^4> and R <^5> represents a hydrogen atom or an organic group of 1-20 carbon atoms each independently.) The aromatic group represented by R <^2> represents Represents an aromatic group having a fluorine atom, and n represents a natural number.)

Positive type photosensitive resin composition as described in a 1st viewpoint whose R <^3> is an organic group which has a sulfonyl group in said Formula (2) from a 2nd viewpoint.

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

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 having 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.)

1st viewpoint thru | or 4 th viewpoint which is a polyimide precursor obtained by superposing | polymerizing the tetracarboxylic acid component and diamine component containing the compound represented by following formula (4), and the said (A) component from 5th viewpoint. Positive type photosensitive resin composition of any one of Claims.

(In formula, R <^7> represents the organic group which has a sulfur atom.).

In a sixth aspect, the tetracarboxylic acid component is a tetracarboxylic acid component containing at least one of the compounds represented by the following formulas (5) to (8) in addition to the compound represented by the formula (4): Positive photosensitive resin composition of description.

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

The positive type photosensitive resin composition as a 7th viewpoint whose 5th or 6th viewpoint which the compound represented by said Formula (4) occupies 40-99 mol% among the said tetracarboxylic acid components.

The positive photosensitive resin composition as described in any one of 5th viewpoint thru | or 7 point which is a diamine component in which the said diamine component contains the diamine compound represented by following formula (9) from an 8th viewpoint.

(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.)

As a ninth viewpoint, the positive photosensitive resin composition according to any one of fifth to eighth aspects, wherein the diamine component is a diamine component containing a diaminosiloxane compound.

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

The positive photosensitive resin composition according to any one of the first to tenth aspects, wherein the solvent (C) is at least one member selected from the group consisting of alcohols or alkyl esters having four or more carbon atoms.

The positive photosensitive resin composition as described in any one of 1st viewpoint-11th viewpoint which contains 0.01-100 mass parts (B) component based on 100 mass parts of (A) component as a 12th viewpoint.

The positive type photosensitive resin composition according to the twelfth point of view, which contains 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 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 and a carbon source. Organic groups of embroidery 1 to 12.)

The positive photosensitive resin composition according to the thirteenth aspect, in which the structure of R ¹⁴ is represented by the following formula (11) in the formula (10).

(Wherein l and k each independently represent 0 or 1, and X ₅ , X ₆ and X ₇ each independently represent a divalent organic having an organic group of 1 to 12 carbon atoms, an oxygen atom, a sulfur atom and a nitrogen atom). Group.)

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

The positive photosensitive resin composition as described in a 15th viewpoint which contains 5-100 mass parts of crosslinking | crosslinked compounds further as (E) component as a 16th viewpoint based on 100 mass parts of (A) component.

The cured film obtained using the positive photosensitive resin composition in any one of 1st viewpoint-16th viewpoint from a 17th viewpoint.

The electronic component which has a cured film of 18th viewpoint from 17th viewpoint.

An organic EL device having the cured film according to the nineteenth viewpoint from the eighteenth viewpoint.

A method of forming a relief pattern in which the positive photosensitive resin composition according to any one of the first to the sixteenth viewpoints is applied on a substrate and heat-dried, and then irradiated with ultraviolet rays to develop a twentieth viewpoint.

Positive Photosensitive Resin Composition

The positive photosensitive resin composition of this invention contains the polyimide precursor which is (A) component or the polyimide obtained from these, and the photoacid generator which is (B) component, These were melt | dissolved in the (C) solvent, respectively, If necessary, respectively It is a composition containing other additives, such as the maleimide compound which is (D) component, the crosslinkable compound which is (E) component, and surfactant.

Hereinafter, each component is explained in full detail.

<(A) component>

(A) A component is a polyimide precursor which has a structural unit represented by following formula (1), or the polyimide obtained from these.

[Formula 9]

In formula (1), n shows the polymerization degree of the polyimide precursor which has a structural unit represented by said formula (1), or the polyimide obtained from these. Although n is a positive integer, when n is larger than 1000, the solubility in a general organic solvent will fall extremely, the viscosity of a resin composition solution may rise remarkably, and handling property may worsen. For this reason, in consideration of solubility, n is preferably a positive integer of 1000 or less, and particularly preferably a positive integer of less than 100.

In addition, the compound of the component (A) may be imidized in a range that is soluble in the developing solution because the reliability of the device may be lowered by adsorption of moisture. The proportion of imidation is preferably 50 to 99.9%, more preferably 60 to 90% from the viewpoint of device reliability and developability.

R <^1> of the said Formula (1) represents the aromatic group represented by following formula (2), and R <^3> shows the organic group which has a sulfur atom in Formula (2).

In formula (2), of R ³ Although the organic group which has a sulfur atom is not specifically limited, From a viewpoint of the solubility of the polymer obtained and the reliability of an element, it is preferable that it is a sulfonyl group, a sulfide group, or a sulfo group.

In formula (2), R <^4> and R <^5> represents a hydrogen atom or a C1-C20 organic group each independently. A method for introducing an organic group having 1 to 20 carbon atoms, wherein the polyimide precursor (A) component or the polyimide obtained therefrom is introduced into the monomer in advance, the polymer and the glycidyl group compound or acryl after polymer formation. You may use the method of making a rate compound react, or the method of adding a primary amine to a reaction solution and forming a salt.

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 halogen groups. These organic groups may be any organic group as long as they are dissolved in a low-pollution organic solvent, but from the viewpoint of the solubility of the polymer to be obtained, a part thereof is preferably substituted with fluorine.

R <^2> of the said Formula (1) represents the aromatic group represented by 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 that satisfies this condition, but is preferably a fluoroalkyl group such as methylene fluoride or trifluoromethyl, It is especially preferable that it is a trifluoromethyl group from a viewpoint of the solubility of the polymer obtained and the reliability of an element.

X <_1> and X <_2> in Formula (3) respectively independently represent a hydrogen atom, the organic device of 1-10 carbon atoms, or a hydroxyl group. Examples of the organic group having 1 to 10 carbon atoms include alkyl group, cycloalkyl group, aromatic group, allyl group, benzyl group, benzoyl group, phenylamide group, or phenyl ester group. It is preferable that it is a hydroxyl group, and it is especially preferable that it is a hydroxyl group from a viewpoint of the photosensitive characteristic.

In addition, the component (A) (a polyimide precursor having a structural unit represented by formula (1) or a polyimide obtained therefrom) comprises a component selected from tetracarboxylic acid and its derivatives (hereinafter referred to as an acid component) and a diamine component. It is a compound obtained by making it react, and also by heat-dehydrating these or chemically dehydrating and imidating.

<Tetracarboxylic acid component>

The acid component used by the polyimide precursor which has a structural unit represented by said Formula (1), or the polyimide obtained from these is represented by the structure of following formula (4). Moreover, the reaction with the diamine component mentioned later converts most to the skeleton represented by said Formula (2).

In formula (4), R <^7> represents the organic group which has a sulfur atom. Although it may be any organic group as long as it has a sulfur atom, it is preferable that it is a sulfonyl group, a sulfide group, or a sulfo group from a viewpoint of the solubility of the polymer obtained and the reliability of an element.

Specific examples of the acid component having a sulfur atom include 3,3 ', 4,4'-diphenylsulfidetetracarboxylic acid component compound, 3,3', 4,4'-diphenylsulfotetracarboxylic acid component compound, 3 Although a 3 ', 4, 4'- diphenyl sulfonyl tetracarboxylic acid component compound etc. are mentioned, It is not limited to these compounds.

In addition, as long as the molar ratio of the acid component having the sulfur atom and the acid component not containing the sulfur atom is in the range of 40/60 to 99/1, the compounds of the two acid components may be used together for copolymerization with the diamine component.

As an acid component which does not contain a sulfur atom, the compound represented by the structure of following formula (5)-(8) is mentioned. These acid components may use two or more kinds when copolymerizing. In particular, the molar ratio of the acid component having sulfur atoms and the acid component not containing sulfur atoms is preferably 50/50 to 80/20 from the viewpoint of reliability of the device.

In formula (5), R <^8> represents the divalent organic group which has the oxygen group directly connected to the organic group or aromatic ring of 1-12 carbon atoms. R ⁸ 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, an aromatic group, and the like. Ether groups, siloxy groups, and the like. Among these, it is preferable that it is a fluoroalkyl group or an ether group from a viewpoint of solubility and photosensitive characteristics, and it is especially preferable that it is a fluoromethyl group from a viewpoint of solubility.

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

In formula (7), R <^9> and R <^10> represents the organic group of 1-12 carbon atoms. R ⁹ and R ¹⁰ may be any organic group, in particular, as long as they are an organic group having 1 to 12 carbon atoms. For example, an alkyl group, a fluoroalkyl group, a cycloalkyl group, an aromatic group, etc. can be mentioned, It is not limited to this.

(8) one, R ¹¹ is a divalent organic group, R ¹² and R ¹³ of carbon atoms from 1 to 12 represents an organic group of 1 to 12 carbon atoms. The divalent organic group having 1 to 12 carbon atoms of R ¹¹ may be a methylene group, an ether group, a trialkylsilyl group or a dialkyldisiloxy group, but the organic group is not particularly limited. R ¹² and R ¹³ are not particularly limited as long as they are an organic group having 1 to 12 carbon atoms, and examples thereof include an alkyl group, a fluoroalkyl group, a cycloalkyl group or an aromatic group.

As a specific example of the acid component which does not contain the sulfur atom represented by the structure of said Formula (5)-(8), 2, 2-bis (3, 4- dicarboxy phenyl) hexafluoro isopypyridene, 4,4 '-Hexafluoroisopropylidenediphthalic acid, pyromellitic acid, 1,2,6,7-naphthalenetetracarboxylic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 3,3 ', 4 , 4'-benzophenonetetracarboxylic acid, 3,3 ', 4,4'-diphenylethertetracarboxylic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid component 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-cyclopentanonetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 5- ( 2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid, 2,3,5-tricarboxy-2-cyclopentanone Acid, bicyclo [2.2.2] octo-7-ene-2,3,5,6-tetracarboxylic acid, 2,3,4,5-tetrahydrofurantetracarboxylic acid, 3,5,6-tricarboxy Alicyclic tetracarboxylic acid components, such as 2-norbornane acetate, are mentioned, but it is not limited to these.

Among the acid components not containing the sulfur atom, 2,2-bis (3,4-dicarboxyphenyl) hexafluoroisopropyridene, 4,4'- especially from the viewpoint of solubility and photosensitivity of the polymer obtained. It is preferable to use hexafluoroisopropylidenediphthalic acid, pyromellitic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid and derivatives thereof, and especially 4,4'-hexa from the viewpoint of solubility of the obtained polymer. It is preferable to use compounds such as fluoroisopropylidenediphthalic dianhydride and dihalide thereof.

<Diamine component>

The diamine component used as the polyimide precursor which has a structural unit represented by said formula (1), or the polyimide obtained from these is represented by the structure of following formula (9).

R ⁶ in formula (9) represents an organic group having 1 to 8 carbon atoms substituted with a fluorine atom, and examples thereof include a dimethylene fluoride group, a trifluoromethyl group, a fluorophenyl group, and the like. If it is not specifically limited, It is preferable that it is a trifluoromethyl group from a viewpoint of the solubility and the photosensitive characteristic of the polymer obtained among these.

X <_3> and X <_4> in Formula (9) represent a hydrogen atom, the C1-C10 organic group, or a hydroxyl group each independently. Examples of the organic group having 1 to 10 carbon atoms include alkyl group, cycloalkyl group, aromatic group, allyl group, benzyl group, benzoyl group, phenylamide group, or phenyl ester group. Or a hydroxy group, particularly preferably a hydroxy group in view of photosensitivity.

Specific examples of the diamine component having an organic group substituted with a fluorine atom in the formula (9) are 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, 2,2-bis (3-amino-4-tolyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 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, 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] hexafluoropropane, and the like, but are not limited thereto. In addition, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 2,2-bis (3-amino-4-tolyl) are suitable compounds in view of solubility and photosensitivity of the obtained polymer. Hexafluoropropane. Especially, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is preferable in the photosensitive characteristic.

Moreover, it can also be used for copolymerization combining the diamine component which does not contain a fluorine atom soluble in the low pollution type organic solvent (component (C)) mentioned later. The other diamine component which does not contain a fluorine atom may be used 2 or more types if at least 1 type of diamine component which has the organic group substituted by the fluorine atom was used.

Specific examples of the diamine component containing no fluorine atom include p-phenylenediamine, m-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl -1,4-phenylenediamine, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, 3,3'-diaminodiphenylether, 4,4'-diaminodi Phenylsulfide, 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'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, benzidine, o- Tolidine, m-tolidine, 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) phene ] Sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy Phenyl] propane, 2,4-diaminophenol, 3,5-diaminophenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis ( 3-amino-4-hydroxyphenyl) ether, bis (4-amino-3-hydroxyphenyl) ether, bis (4-amino-3,5-dihydroxyphenyl) ether, bis (3-amino-4 -Hydroxyphenyl) methane, bis (4-amino-3-hydroxyphenyl) methane, bis (4-amino-3,5-dihydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) Sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (4-amino-3,5-dihydroxyphenyl) sulfone, 4,4'-diamino-3,3'-dihydroxy ratio Phenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'- Dimethoxybiphenyl, 1,4-bis (3-amino-4-hydroxyphenoxy) benzene, 1,3-bi (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, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1,3-benzenedicarboxylic acid, 2,5-diamino-1,4-benzenedicarboxylic acid, bis ( 4-amino-3-carboxyphenyl) ether, bis (4-amino-3,5-dicarboxyphenyl) 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 Ci) phenyl] sulfone or bis [4- (4-amino-3-carboxyphenoxy) phenyl] propane.

Moreover, in order to improve the adhesiveness to the board | substrate of the coating film produced using the positive photosensitive resin composition containing the polyimide precursor which has a structural unit represented by said Formula (1), or the polyimide obtained from these, it is a diaminosiloxane as a part of diamine component. The compound can be used in combination. As such siloxane containing diamine, bis (3-aminoalkyl) -1,1,3,3-tetramethyldisiloxane is preferable, and bis (3-aminopropyl) -1,1 from the viewpoint of adhesiveness and solubility with a substrate. , 3,3-tetramethyldisiloxane is more preferred.

The siloxane-containing diamine is preferably used in a molar ratio of 1 to 30% of the total molar amount of the diamine component in terms of adhesion to the substrate and developability. When it exceeds 30 mol%, developability will fall and a residue will remain easily on a board | substrate. More preferably, it is 1-20 mol%, It is still more preferable to use 1-10 mol%.

<(B) component>

The photoacid generator as component (B) is particularly limited as long as it has a function of generating acid directly or indirectly by irradiation of light used for exposure and enhancing solubility of the light irradiation part into an alkali developer. It doesn't work. Moreover, a photo-acid generator can also be used 1 type or in combination of 2 or more types.

As the photoacid generator as the component (B), all conventionally known photoacid generators may be applied, and specific examples thereof include o-quinonediazide compounds, allyl diazonium salts, diallyl iodonium salts, triallyl sulfonium salts, and o-. Nitrobenzyl ester, p-nitrobenzyl ester, trihalomethyl group substituted s-triazine derivative, imide sulfonate derivative, etc. are mentioned.

In addition, a sensitizer can be used together with the photo-acid generator which is (B) component as needed. Examples of such sensitizers include, but are not limited to, perylene, anthracene, thioxanthone, mihiraketone, benzophenone or fluorene.

Among the photoacid generators as the component (B), an o-quinone diazide compound is preferable in that a high sensitivity and high resolution can be obtained from a coating film obtained by using a positive photosensitive resin composition.

The o-quinone diazide sulfide compound is usually o-quinone diazide sulfonic acid ester or o- by condensation reaction of o-quinone diazide sulfonyl 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 with quinonediazidesulfonamide.

As o-quinone diazide sulfonic-acid component which comprises said o-quinone diazide sulfonyl chloride, for example, 1, 2- naphthoquinone- 2- diazide- 4-sulfonic acid, a 1, 2- naphthoquinone- 2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2- diazide-6-sulfonic acid, etc. are mentioned.

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' '-trihydroxy Triphenylmethane, 1,1,1-tris (4-hydroxyphenyl) ethane, 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethyl Lidene] bisphenol, 3,4,5-trihydroxy methyl benzoate, 3,4,5-trihydroxy benzoic acid propyl, 3,4,5-trihydroxy benzoic acid isoamyl ester, 3,4,5-tri Hydroxybenzoic acid-2-ethyl butyl ester, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2, Phenolic compounds such as 3,4,4'-tetrahydroxybenzophenone, 2,3,4,2 ', 4'-pentahydroxybenzophenone, ethanol, 2-propanol, 4- Tanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate, butyl lactate, etc. And aliphatic alcohols.

Moreover, as a compound which has the said amino group, aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, p-phenyl Aniline, such as a rendiamine, 4,4'- diamino diphenylmethane, 4,4'- diamino diphenyl ether, an aminocyclohexane, etc. are mentioned.

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, and 2,4-diaminophenol. , 4,4'-diamino-4 ''-hydroxytriphenylmethane, 4-amino-4 ', 4' '-dihydroxytriphenylmethane, bis (4-amino-3-carboxy-5-hydrate Hydroxyphenyl) ether, bis (4-amino-3-carboxy-5-hydroxyphenyl) methane, bis (4-amino-3-carboxy-5-hydroxyphenyl) sulfone, 2,2-bis (4-amino Aminophenols such as 3-carboxy-5-hydroxyphenyl) propane, 2,2-bis (4-amino-3-carboxy-5-hydroxyphenyl) hexafluoropropane, 2-aminoethanol, 3-amino Alkanolamines, such as a propanol and 4-amino cyclohexanol, are mentioned.

Condensation reaction of o-quinonediazidesulfonyl chloride with a compound having at least one selected from a hydroxy group and an amino group results in some or all of the hydroxy or amino group of the compound being o-quinonediazide of o-quinonediazidesulfonylchloride. O-quinone diazide compounds of the di-, tri-, tetra-, or 5-substituted substituents substituted with sulfonyl groups can be obtained. When the o-quinone diazide compound is used as a component of the positive photosensitive resin composition, the above-mentioned o-quinone diazide compound of the polysubstituted compound may be used alone or in the form of two or more poly-substituted compounds selected from the above-mentioned polysubstituted compounds. It is common to use in mixtures.

Among the o-quinone diazide compounds described above, in the coating film obtained by using the positive photosensitive resin composition, the development residue at the bottom of the pattern during development (residue of the pattern edge part) while the balance of the difference in the development solubility between the exposed portion and the unexposed portion is good. O-quinonediazidesulfonic acid esters of p-cresol and 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol o-quinone diazide sulfonic acid ester, o-quinone diazide sulfonic acid ester of methyl 3,4,5-trihydroxybenzoate, o-quinone diazide sulfonic acid ester of 2,3,4-trihydroxybenzophenone, or 2 O-quinonediazidesulfonic acid esters of, 3,4,4'-tetrahydroxybenzophenone and the like are preferable, and these compounds may be used alone or in combination of two or more kinds arbitrarily selected from these compounds. .

Content of the photo-acid generator which is (B) component used for this invention is 0.01-100 mass parts based on 100 mass parts of (A) component. In the coating film obtained from the positive type photosensitive resin composition of this invention, the balance of the difference of the solubility of the developing solution of an exposed part and an unexposed part becomes favorable, and from a viewpoint of the sensitivity of this coating film and the mechanical characteristics of the cured film obtained from this coating film, (B) component 50 mass parts or less are especially preferable, and, as for content of a phosphorus photoacid generator, it is more preferable that it is 30 mass parts or less.

<(C) component>

Examples of the solvent (C) used in the positive photosensitive resin composition of the present invention include the high solubility of component (A) (polyimide precursor having a structural unit represented by formula (1) or polyimide obtained from these), ( B) alcohols or alkyl esters having four or more carbon atoms in terms of good compatibility with components (photoacid generators) and other components described later, and easy handling in positive type photosensitive resin compositions, and low organic solvents. Is preferred. Representative solvents include butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, γ-butyrolactone, ethyl lactate, butyl lactate, n-butanol, sec-butanol, t-butanol, methoxymethylpentanol, methylcellulose solution, ethylcellulose solution, methylcellosolve acetate, ethylcellosolve 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 monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether , Dipropylene glycol monoacetate monopropyl ether, 2-ethoxyethanol, 2-butoxy 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, methyl ethyl 3-ethoxypropionate And ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate or butylbutyrate. These solvents may be two or more types of mixed solvents.

In particular, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, γ-butyrolactone, ethyl lactate and lactic acid from the viewpoint of the easiest handling in the positive photosensitive resin composition. Preference is given to using one kind or a mixture of two or more kinds selected from the group consisting of butyl.

In addition to the above solvents, acetone, methanol, ethanol, isopropyl alcohol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl iso amyl 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, dioxane, N, N-dimethylacetamide, N, N-dimethyl Formamide, N-methyl-2-pyrrolidone, N-vinylpyrrolidone, dimethyl sulfoxide, n-methylpyrrolidone, n-hexane, n-pentane, n-octane, 2-methoxyethanol, di Ethyl ether, cyclohexanone, 3-e You may use it, mixing solvents, such as oxypropionic acid, 3-methoxypropionic acid, or diglyme. However, these other solvents are preferably used in view of the fact that they are used in conventional positive photosensitive resin compositions (not low-pollution organic solvents).

<(D) component>

The positive photosensitive resin composition of this invention can contain a maleimide compound as (D) component. The maleimide compound as the component (D) is not particularly limited as long as it is a compound soluble in the alkali developer in the developing step of the coating film obtained by using the positive photosensitive resin composition of the present invention. The maleimide compound as the 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.

The compound represented by following formula (10) can be mentioned as a maleimide compound which has a structure in which the above-mentioned maleimide site | part is directly connected to the aromatic ring and the hydrogen atom is directly connected to the adjacent aromatic carbon.

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 An organic group of 1 to 12 carbon atoms is shown.

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

In Formula (11), l and k each independently represent 0 or 1, and X ₅ , X ₆ and X ₇ each independently have an organic group having 1 to 12 carbon atoms, an oxygen atom, a sulfur atom and a nitrogen atom. A divalent organic group is shown.

In particular, in said Formula (11), l and k are 1, X <_5> and X <_7> are oxygen atoms, and X <_6> is a dimethylmethyl group.

As a specific example of the maleimide compound which is (D) component represented by said Formula (10), 2, 2-bis (3-amino- 4-maleimide) hexafluoro propane, 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'- dimaleimide diphenylmethane, 4,4-methylene-bis (2-methylmaleimide), 4,4'- dimaleimide diphenyl sulfone , 3,3'-dimaleimide diphenylsulfone, 1,4'-bis (4-maleimidephenoxy) benzene, 1,3'-bis (4-maleimidephenoxy) benzene, 1,3'- Bis (4-maleimidephenoxy) benzene, bis [4- (4-maleimidephenoxy) phenyl] sulfone, bis [4- (3-maleimidephenoxy) phenyl] sulfone, bis [3- (4- Maleimidephenoxy) phenyl] sulfone, bis [3- (3-maleimidephenoxy) phenyl] sulfone, 2,2'-bis [4- (4-maleimidephenoxy) phenyl] propane, 2,2- Bis [4- And compounds such as (3-aminophenoxy) phenyl] propane, but are not limited thereto.

Among the above compounds, 4,4'-dimaleimide diphenyl methane and 2,2'-bis [4- (4-maleimidephenoxy) phenyl] propane are preferable in terms of easy availability, and the viewpoint of photosensitivity is also preferred. More preferably 2,2'-bis [4- (4-maleimidephenoxy) phenyl] propane.

The maleimide compound which is (D) component in this invention can be used in combination of 2 or more type.

Although content of the maleimide compound which is (D) component in the positive photosensitive resin composition of this invention is not specifically limited, 5-100 mass parts is preferable based on 100 mass parts of polyimide precursors which are (A) component, and 5-20 It is more preferable that it is a mass part.

<(E) component>

The positive photosensitive resin composition of this invention can contain a crosslinkable compound as (E) component. The crosslinkable compound as the component (E) is a polyimide precursor as the component (A) in the step of converting a coating film obtained by using the positive photosensitive resin composition of the present invention to a cured film (hereinafter referred to as final curing), or (B It will not specifically limit, if it is a compound which has the group which can react with the organic group contained in at least one of the photo-acid generators which is a component.

As a crosslinkable compound which is (E) component, for example, the compound containing two or more epoxy groups, or the melamine derivative | guide_body, benzoguanamine derivative | guide_body, or glycol in which the hydrogen atom of an amino group has the group substituted by methylol group, the alkoxy methyl group, or both. Us etc. can be mentioned. The melamine derivatives and benzoguanamine derivatives may be dimers or trimers, or mixtures arbitrarily selected from monomers, dimers and trimers. As these melamine derivatives and the benzoguanamine derivative | guide_body, it is preferable to have a methylol group or an alkoxy methyl group in average of 3 or more and less than 6 per triazine ring.

In addition, in this invention, the crosslinking | crosslinked compound which is (E) component can be used in combination of 2 or more types.

As a crosslinking | crosslinked compound which is (E) component, it is preferable to use a commercially available compound from an easy point of acquisition. Although the specific example (brand name) is shown below, it is not limited to this.

Compounds containing two or more epoxy groups include epoxide GT-401, epoxide GT-403, epoxide GT-301, epoxide GT-302, ceroxide 2021, ceroxide 3000 (or more) Epoxy compounds having a cyclohexene structure such as Gakuko Industries Co., Ltd., Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004, Epicoat 1007, Epicoat 1009, Epicoat 1010, Epicoat 828 (or more) Bisphenol A type epoxy compounds such as Japan epoxy resin Co., Ltd. and bisphenol F type epoxy compounds such as Epicoat 807 (manufactured by Japan Epoxy Resin Co., Ltd.), epicoat 152, epicoat 154 (above, Japan epoxy resin) Phenol novolak type epoxy compounds such as EPPN201, EPPN202 (above, Nihon Kayaku Co., Ltd.), ECON-102, ECON-103S, ECON-104S, ECON-1020, ECON-1025, ECON- Cresol novolak-type epoxy compounds such as 1027 (manufactured by Nihon Kayaku Co., Ltd.) and Epicoat 180S75 (manufactured by Japan Epoxy Resin Co., Ltd.), Denacol EX-252 (Nagase Chem) Corporation made), CY175, CY177, CY179, Araldite CY-182, Araldite CY-192, Araldite CY-184 (above, made by CIBA-GEIGY AG), epicron 200, epicron 400 (Above, Dainihonki Kagaku Kogyo Co., Ltd.), epi coat 871, epi coat 872 (above, Japan epoxy resin Co., Ltd.), ED-5661, ED-5662 (above, Celane coating) Alicyclic epoxy compounds, such as 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 (above, Nagase Chemtex Co., Ltd.).

Melamine derivatives, benzoguanamine derivatives or glycolurils in which the hydrogen atom of the amino group has a methylol group, an alkoxymethyl group or a group substituted on both sides thereof are MX-750 and triazine ring 1 in which an average of 3.7 methoxymethyl groups are substituted per triazine ring. MW-30 (above, manufactured by Sanwa Chemical) having an average of 5.8 methyl groups per group, 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, Cymel 254, etc. Butoxymethylated melamine such as melamine, cymel 506, cymel 508, carboxyl group-containing methoxymethyl isobutoxymethylated melamine such as cymel 1141, methoxymethylated ethoxymethylated benzoguanamine such as cymel 1123, cymel 1123 Methoxymethylation such as -10 Butoxymethylated benzoguanamine, such as methoxymethylated benzoguanamine, cymel 1128, and carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine, such as cymel 1125-80 (above, Nihon Cytech Industries Co., Ltd. Mitsui cyanamide)), butoxy methylation glycoluril like Cymel 1170, methylolation glycoluril like Cymel 1172, etc. are mentioned.

The content of the crosslinkable compound which is the (E) component of the positive photosensitive resin composition of the present invention is not particularly limited, but from the viewpoint of the storage stability of the positive photosensitive resin composition, the absorptivity of the resulting cured film, and the heat resistance and chemical resistance ( 5-100 mass parts is preferable based on 100 mass parts of polyimide precursor which is A) component, and it is preferable that it is 5-20 mass parts from a viewpoint of storage stability.

<Other additives>

In addition, the positive photosensitive resin composition of the present invention may be a co-adjuvant such as a surfactant, a rheology modifier, a silane coupling agent, a pigment, a dye, a storage stabilizer, an antifoaming agent, or a polyhydric phenol as necessary, so long as the effects of the present invention are not impaired. And accelerators such as polycarboxylic acid.

Surfactants which can be used for the purpose of improving the applicability of the positive photosensitive resin composition of the present invention include fluorine-based surfactants, silicone-based surfactants, nonionic surfactants and the like. As this kind of surfactant, commercial items, such as those made by Sumitomo 3M Co., Ltd., Dainihon Inky Kagaku Kogyo Co., Ltd., or Asahi Glass Co., Ltd., can be used, for example. These commercial items are good because they can be easily obtained. Specific examples thereof include F-top EF301, EF303, EF352 (manufactured by Jemuco Co., Ltd.), Mechafax F171, F173 (manufactured by Dainiphon Inki Kagaku Kogyo Co., Ltd.), Flora FC430, FC431 (Sumitomo 3M Corporation). And fluorine-based surfactants such as Asahi Guard AG710, Safron S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by Asahi Glass Co., Ltd.).

The said surfactant can be used individually by 1 type or in combination of 2 or more types.

In addition, when surfactant is used, the content is 0.2 mass% or less normally in 100 mass% of positive type photosensitive resin compositions, Preferably it is 0.1 mass% or less. Even if the amount of the surfactant used is set to an amount exceeding 0.2% by mass, the effect of improving the applicability is slowed and it is not economical.

<Positive Photosensitive Resin Composition>

The positive type photosensitive resin composition of this invention contains the polyimide precursor which is (A) component or the polyimide obtained from these, the photoacid generator which is (B) component, and (C) solvent, respectively, It is a composition which can further contain one or more of other additives, such as a maleimide compound, the crosslinking | crosslinked compound which is (E) component, and surfactant.

Among these, the preferable example of the positive photosensitive resin composition of this invention is as follows.

[1]: Positive type photosensitive resin composition containing 0.01-100 mass parts (B) component based on 100 mass parts of (A) component, and these components melt | dissolving in (C) solvent.

[2]: Positive type photosensitive resin composition which contains 5-100 mass parts of (D) component further based on 100 mass parts of (A) component to the composition of said [1].

[3]: Positive type photosensitive resin composition which contains 5-100 mass parts of (E) component further based on 100 mass parts of (A) component to the composition of said [2].

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 is generally positive photosensitive sensitivity having a concentration arbitrarily selected in the range of 1 to 50 mass% of solid content concentration. A coating film can be formed easily by making the solution of a resin composition. Solid content means here the thing remove | excluding the (C) solvent from all the components of a positive photosensitive resin composition.

The preparation method of the positive photosensitive resin composition of this invention is not specifically limited. Since this kind of composition is usually used in the form of a solution, the positive type photosensitive resin composition of the present invention generally contains (A) component, (B) component and (D) component and (E) component as needed. A method of dissolving in a solvent to form a uniform solution, or a method of further adding and mixing other additives at a suitable stage of the preparation method.

In the preparation of the positive photosensitive resin composition of the present invention, in the preparation of component (A), that is, a reaction solution obtained by polymerizing a component selected from tetracarboxylic acid and its derivatives with a diamine component in an organic solvent can be used as it is. It may be. Moreover, the solvent described in the above-mentioned (C) solvent is mentioned as an organic solvent used at this time. In this case, when the (B) component or the like is added to the reaction solution of the component (A) in the same manner as described above, the solution (C) may be further added for the purpose of concentration preparation. And the (C) solvent used for concentration adjustment with the organic solvent used at the time of manufacture of (A) component may be same or different.

In the case of using plural kinds of organic solvents, the plural kinds of organic solvents may be used in combination, and the plural kinds of organic solvents may be optionally added.

And it is preferable to use the solution of the prepared positive photosensitive resin composition after filtering using the filter etc. which are about 0.2 micrometer in diameter.

<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 or an oxide film or a nitride film by, for example, a known method such as spin coating, dipping and printing. The coating film which consists of positive type photosensitive resin composition of this invention can be formed by predrying at the temperature of 60 degreeC-160 degreeC, Preferably it is 70 degreeC-130 degreeC.

After the coating film is formed, for example, the coating film is exposed using a mask having a predetermined pattern with ultraviolet light or the like, and developed with an alkali developer, so that the exposed portion is washed away, whereby a relief pattern having a sharp cross section is formed on the substrate.

The alkaline developer used herein is not particularly limited as long as it is an alkaline aqueous solution, and for example, an aqueous solution of alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate, hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline. Amine aqueous solutions, such as aqueous solution of quaternary ammonium, ethanolamine, propylamine, and ethylenediamine, etc. are mentioned.

The concentration of the alkaline developer is generally 10% by mass or less, and industrially, an alkaline aqueous solution of 0.1 to 3.0% by mass is used. The alkali developer may also contain alcohols, surfactants, and the like, each of which preferably contains about 0.05 to 10% by mass.

In the developing step, the temperature of the alkaline developing solution can be arbitrarily selected, but in the case of using the positive photosensitive resin composition of the present invention, since the solubility of the exposed part is high, development by the alkaline developing solution can be easily performed at room temperature.

By heat-processing (baking) the board | substrate which has the obtained relief pattern at the temperature of 180 degreeC-400 degreeC, the cured film which has the relief pattern which is low in water absorption and excellent in electrical characteristics and also excellent in heat resistance and chemical resistance is obtained.

Since the cured film obtained from the positive photosensitive resin composition of this invention has such an outstanding effect, it can be used for an electric / electronic device, a semiconductor device, a display device, etc. In particular, the cured film obtained from the positive type photosensitive resin composition of the present invention has a characteristic effect of high reliability of the organic EL device (a kind of LED), and thus the damage of the organic light emitting device is a problem. Ion migration of copper wiring in insulating films and barrier ribs or in semiconductor packages is very useful in buffer codes where the absorption of insulating films is greatly affected.

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

Abbreviation symbol used in the Examples

Meaning 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-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

<Tetracarboxylic acid component>

6FDA: 4,4'-hexafluoroisopropylidenediphthalic anhydride

DSDA: 3,3'-4,4'-diphenylsulfontetracarboxylic 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

γ-BL: γ-butyrolactone

<Mine generator>

P200: P-200 (brand name) 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1methylethyl] phenyl] ethylidene] bisphenol 1 mol by Toyo Segogyo Co., Ltd. make Photosensitive agent synthesized by condensation reaction with 2 moles of 1,2-naphthoquinone-2-diazide-5-sulfonylchloride

<Maleimide component>

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

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

According to the synthesis examples below, the weight average molecular weight (hereinafter referred to as Mw) and molecular weight distribution of the polymer were measured using Nippon Bunco Co., Ltd. GPC apparatus (Shodex® columns KF803L and KF805L) as the elution solvent. It measured on the conditions that it put in a column (column temperature: 50 degreeC), and eluted at a flow volume of 1 ml / min. In addition, Mw is represented by polystyrene conversion value.

[Measurement of imidization rate]

The imidation ratio was measured by H-NMR using an NMR apparatus (JNM-LA series, manufactured by Nippon Denshi Co., Ltd.) and calculated from the proton ratio of the aromatic proton ratio of the polymer skeleton and the NH portion of the polyamic acid.

Synthesis Example

Preparation of Polyamic Acid Solution (Synthesis Example 1)

BAHF 26.6 g (0.199 mol), APDS 5.51 g (0.0022 mol), and DSDA 71.5 g (0.199 mol) were dissolved in 850 g of PGME, and the concentration was 15 wt%, followed by reaction at 60 ° C for 24 hours. Obtained polymer Mw was 8600 and molecular weight distribution was 1.55. 1.00 g of this obtained polymer solution was put into an aluminum cup, and the solid content was calculated by heating on a hot plate for 2 hours. Solid content concentration of the obtained solid content was 16.39 wt%. Furthermore, this polymer was precipitated in 50 wt% methanol aqueous solution of 8 times (4000 g) of polymer solutions, and it dried under reduced pressure, and obtained polyamic-acid powder. The yield of the obtained polymer was 91% and the imidation ratio was 62%. In addition, the obtained polymer was soluble in PGME and PGMEA.

<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 15wt%, and polymers were synthesized using the same method as in Synthesis Example 1. Table 1 shows the diamine, acid dianhydride and solvent used, the Mw and molecular weight distribution of the polymer obtained, the solid content concentration and imidation ratio of the polymer solution obtained. These polymers were also soluble in PGMEA.

<Production 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, and the precipitate was filtered and dried under reduced pressure to obtain a polyamic acid. Table 1 shows the amount of diamine, acid dianhydride and solvent used, the Mw and molecular weight distribution, solid content concentration and imidation ratio of the obtained polymer. Since the obtained polymer was insoluble in either PGME or PGMEA, the reaction solution was used for preparation of the positive photosensitive resin composition which follows next.

Moreover, the polymer was synthesize | combined in PGME which melt | dissolved various diamines like the synthesis example 1, and the polymer precipitated 1 hour after reaction.

[Table 1] Polymer Composition

Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 Polyamic acid (partly 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 in preparation * 2: Solid content concentration of reaction solution

[Production of Positive Photosensitive Resin Composition: Examples 1 to 3, Comparative Examples 1 to 4]

According to the composition shown in following Table 2, (A) component, (B) component, (C) solvent, (D) component, and a fluorine-type surfactant (Dainihon Inkaki Chemical Co., Ltd. make, Mekafax R-30 The positive photosensitive resin composition of each Example and each comparative example was prepared by mixing 0.0002g) in a predetermined ratio, and stirring at room temperature for 3 hours or more to make a uniform solution.

TABLE 2 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

[Photosensitive Characterization: Examples 1 to 3, Comparative Examples 1 to 4]

In each of the positive photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 4 obtained, photosensitive characteristics were evaluated by the following method. The results obtained are shown in Table 3.

<1. Film thickness before heat treatment (firing)

The positive photosensitive resin composition was applied onto the ITO substrate (manufactured by Sanyo Shinku Kogyo Co., Ltd.) having a step of 25 mm x 25 mm using a spin coat, and then prebaked on a hot plate at a temperature of 100 ° C for 120 seconds to form a coating film. In addition, the film thickness was measured using the contact type film thickness gauge (Dektak 3ST by ULVAC Co., Ltd.).

<2. Post-development film thickness, resolution (line width)>

Infrared light was irradiated to the obtained coating film for 11 second (70mJ / cm <^2> ) by the Canon irradiation company PLA-501 through the mask of the line / space of 100 micrometers / 200 micrometers. After exposure, the solution was immersed in 23 ° C. aqueous tetramethylammonium hydroxide solution (the aqueous solution concentration used in each example is shown in Table 3) for 30 seconds to develop and the film thickness after development was measured.

Furthermore, the coating film after image development was observed with the optical microscope, and the minimum line width in which the line / space was formed without pattern peeling was made into the resolution.

<3. Film thickness after heat treatment (firing)>

In the same manner as in <1.>, the photosensitive resin coating film formed on the stepped ITO substrate was heated at 100 ° C on a hot plate for 120 seconds. Next, after heating at 230 degreeC for 30 minutes, without exposing, the film thickness was measured.

[Table 3] Evaluation of Photosensitive Characteristics

NO. Film thickness before heat treatment (㎛) Developer concentration (23 ℃, mass%) Post-development film thickness (㎛) Resolution (μm) Film thickness after heat treatment (㎛) 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. Device characteristic evaluation: Examples 1 to 3, Comparative Examples 1 to 4>

UV ozone cleaning apparatus (Techno Co., Ltd.) was obtained by applying the polyimide pattern obtained in <2.> (Also, in Comparative Example 4, since the pattern was completely dissolved after development, the polyimide film was obtained without application after development on the stepped ITO substrate). After rinsing for 40 minutes with a vision agent), ND-1032 (manufactured by Nissan Kagaku Kogyo Co., Ltd.) was applied by spin coating, and heat-treated (fired) at 200 ° C for 1 hour on a hot plate to obtain a film having a thickness of 30 nm. Thereafter, 15 mm ² squares were cut out at the center, and under vacuum conditions, devices were fabricated by depositing α-NPD, Alq 3, FLi, and Al in the order of device components. The vapor deposition component was measured by crystal oscillation film-forming controller CRTM-6000 (manufactured by Nihon Shinkugi Jutsu Co., Ltd.). Thereafter, an electric current of 9 V was supplied to the device, and the light emitting surface was observed with an optical microscope. Table 4 shows the evaluation results of the device components, the deposition amount and the light emitting surface.

[Table 4] Evaluation results of device characteristics

Yes Polyimide α-NPD (nm) Alq3 (nm) FLi (nm) Al (nm) Evaluation of 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 ◎: Clear light emission can be seen at the edge part.

                (Circle): A blur exists in a part of the interface of an edge part and a light emitting surface.

                (Triangle | delta): A bleeding exists in the whole interface of an edge part and a light emitting surface.

                 X: A shadow exists in the interface of an edge part and a light emitting surface.

[Device evaluation result]

In the device using P1 or P2, the edges of the polyimide pattern were clearly seen. This indicates that the partition element using the polyimide of Examples 1 to 3 can produce pixels without adversely affecting the light emitting surface.

On the other hand, in the device using HP1 to HP4, there was a poor light emission due to the presence of shadows at the interface between the polyimide pattern edge and the light emitting surface. The result was a concern.

The positive photosensitive resin composition of the present invention is uniformly dissolved in a solvent such as propylene glycol monomethyl ether acetate (PGMEA) used in a low-polluting organic solvent, for example, a photoresist material, and has a degree of trouble at the time of development. It is possible to form a fine pattern without the film reduction of the miner. In addition, it is possible to obtain the effect that the organic EL element using the film cured after pattern formation displays a clear light emitting surface without shadow.

Claims (20)

The polyimide precursor which has a structural unit represented by following formula (1) as (A) component, or the polyimide obtained from these, and the compound which generate | occur | produces an acid by light in (B) component are contained, These are contained in (C) solvent Dissolved positive photosensitive resin composition. [Formula 1]

(In Formula (1), R ¹ is Formula (2). [Formula 2]

(In formula (2), R <^3> represents the organic group which has a sulfur atom, R <^4> and R <^5> represents a hydrogen atom or an organic group of 1-20 carbon atoms each independently.) The aromatic group represented by R <^2> represents Represents an aromatic group having a fluorine atom, and n represents a natural number.) The method of claim 1, Positive type photosensitive resin composition whose said R <^3> is an organic group which has a sulfonyl group in said Formula (2). The method according to claim 1 or 2, In the formula (2), at least one of R ⁴ and R ⁵ is a hydrogen atom, the positive photosensitive resin composition. The method according to any one of claims 1 to 3, The positive photosensitive resin composition which has a structure in which R <^2> is represented by following formula (3) in said Formula (1). [Formula 3]

(Wherein R ⁶ represents an organic group having 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.) The method according to any one of claims 1 to 4, Positive type photosensitive resin composition whose said (A) component is a polyimide precursor obtained by superposing | polymerizing the tetracarboxylic acid component and diamine component containing the compound represented by following formula (4), or a polyimide obtained from these. [Formula 4]

(In formula, R <^7> represents the organic group which has a sulfur atom.). The method of claim 5, Positive type photosensitive resin composition whose said tetracarboxylic-acid component is the tetracarboxylic-acid component containing at least 1 sort (s) of the compound represented by following formula (5)-formula (8) in addition to the compound represented by said Formula (4). [Formula 5]

(Wherein m represents 0 or 1, R ⁸ represents a divalent organic group having 1 to 12 carbon atoms or an oxygen atom directly connected to an aromatic ring, and R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are Each represents an organic group having 1 to 12 carbon atoms.) The method according to claim 5 or 6, Positive type photosensitive resin composition in which the compound represented by the said Formula (4) occupies 40-99 mol% among the said tetracarboxylic acid components. The method according to any one of claims 5 to 7, The positive photosensitive resin composition whose diamine component is a diamine component containing the diamine compound represented by following formula (9). [Formula 6]

(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.) The method according to any one of claims 5 to 8, The positive photosensitive resin composition whose said diamine component is the diamine component containing a diaminosiloxane compound. The method according to any one of claims 1 to 9, The positive photosensitive resin composition whose said (B) component is a naphthoquinone diazide sulfonic-acid ester compound. The method according to any one of claims 1 to 10, Positive type photosensitive resin composition whose said (C) solvent is at least 1 sort (s) chosen from the group which consists of alcohol or alkyl ester which has 4 or more carbon atoms. The method according to any one of claims 1 to 11, Positive type photosensitive resin composition containing 0.01-100 mass parts (B) component based on 100 mass parts of (A) component. The method of claim 12, Positive type photosensitive resin composition which contains 5-100 mass parts of maleimide compounds represented by following (10) further as (D) component based on 100 mass parts of (A) component. [Formula 7]

In the formula, 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 and a carbon source. Organic groups of embroidery 1 to 12.) The method of claim 13, The formula (10), positive-tone light blocking resin composition having the structure R ¹⁴ is represented by the following formula (11). [Formula 8]

(Wherein l and k each independently represent 0 or 1, and X ₅ , X ₆ and X ₇ each independently represent a divalent organic having an organic group of 1 to 12 carbon atoms, an oxygen atom, a sulfur atom and a nitrogen atom). Group.) The method of claim 14, In the formula (11), l and k are 1, X ₅ and X ₇ are oxygen atoms, and X ₆ is a dimethylmethyl group. The method of claim 15, Positive type photosensitive resin composition which contains 5-100 mass parts of crosslinking | crosslinked compounds as (E) component further based on 100 mass parts of (A) component. The cured film obtained using the positive photosensitive resin composition of any one of Claims 1-16. The electronic component which has a cured film of Claim 17. The organic electroluminescent element which has a cured film of Claim 18. The method of forming a relief pattern which is developed by applying ultraviolet light after applying the positive photosensitive resin composition according to any one of claims 1 to 16 on a substrate and heat drying.