JP2010243748A - Photosensitive resin composition, and method of manufacturing heat-resistant resin film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition hardly causing appearance defects. <P>SOLUTION: The photosensitive resin composition contains (a) a polyimide resin or its precursor, (b) a quinone diazide compound, (c) a solvent and (d) a surfactant, wherein the surfactant (d) contains (d1) a silicon-based surfactant and (d2) a surfactant containing a fluorine atom, the contents X mass% and Y mass% of (d1) and (d2), respectively, in the photosensitive resin composition satisfy X>Y (Y≠0), and the whole amount of the surfactant (d) lies in a range of ≥0.005 mass% and ≤0.10 mass% in the photosensitive resin composition. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition and a method for producing a heat resistant resin film. More specifically, the present invention relates to a photosensitive resin composition suitable for an insulating layer of an organic electroluminescent device, a surface protective film of a semiconductor element, an interlayer insulating film, and the like, and a method for producing a heat resistant resin film.

  As a flat panel display, a liquid crystal display (LCD) is widely used. Recently, a light emitting flat panel display such as a plasma display panel (PDP) or an electroluminescence (EL) display has been attracting attention. In particular, organic EL displays are actively researched and developed as full-color displays that can be made ultra-thin because they can achieve high brightness with low power consumption and do not require a backlight.

  A photosensitive resin composition is known as a material for forming an insulating layer of an organic EL display. Among them, the positive photosensitive resin composition is most suitable for the insulating layer because it has a forward tapered shape in cross section, and is widely used. However, in the manufacturing process from application of the insulating layer to drying of the coating film, there is a problem that uneven pin marks are generated in the insulating layer and the product quality is lowered. Here, the pin mark unevenness means that the shape of an object that is close to or in contact with the heated object remains as an unevenness that can be visually confirmed on the heated object. For example, when the photosensitive resin composition is applied to a support substrate and heated by a hot plate and dried, the support substrate to which the photosensitive resin composition is applied is held on a jig such as a proxy pin and heated. At that time, pin mark unevenness often appears in a portion in contact with the proxy pin. The generated pin mark unevenness impairs the uniformity of the thickness of the insulating layer after curing, and causes problems such as deterioration of display quality when finally formed into a panel. In particular, the photosensitive resin composition containing polyimide or a polyimide precursor widely used as an insulating layer often developed pin mark unevenness.

As a countermeasure against uneven pin marks by remodeling the heating device, a second substrate that can be moved up and down that is held at a predetermined temperature of the hot plate is placed on a substrate on which a resist is applied from the transport section when it is raised and is in a lowered state. A resist baking apparatus provided with a hot plate has been proposed (see, for example, Patent Document 1). Also, a synthetic resin pin used in a hot plate type proximity bake furnace, or a holding member that holds the heated body when the heated body is heated using a heating source, A heated body holding member having a cross-sectional area S ₁ of 2.0 mm ² or less has been proposed (see, for example, Patent Documents 2 to 3).

  On the other hand, as a photosensitive resin composition that hardly causes pin mark unevenness, a photosensitive resin composition containing an organic solvent having a boiling point of 100 ° C. to 140 ° C. under atmospheric pressure in a total amount of 50% by weight to 100% by weight. A thing is proposed (for example, refer to patent documents 4). Moreover, the photosensitive resin composition containing a silicon-type surfactant and a fluorine-type surfactant is proposed (for example, refer patent documents 5-9).

JP-A-8-236431 JP-A-8-279548 JP 2002-40223 A JP 2004-54254 A JP 11-349810 A JP 2005-284114 A JP 2006-184908 A JP 2007-114763 A JP 2008-7744 A

  However, even when the above technique is used, when a heat-resistant resin film is formed using a photosensitive resin composition containing a polyimide resin or a precursor thereof, the coating film of the photosensitive resin composition is particularly dried under reduced pressure. At the time, there was a problem that appearance defects such as pin mark unevenness and moyare unevenness occurred. In view of the above problems, an object of the present invention is to provide a photosensitive resin composition that hardly causes appearance defects.

  The present invention is a photosensitive resin composition comprising (a) a polyimide resin or a precursor thereof, (b) a quinonediazide compound, (c) a solvent, and (d) a surfactant, and (d) a surfactant. Includes (d1) a silicon-based surfactant and (d2) a surfactant having a fluorine atom, the content of (d1) in the photosensitive resin composition is X mass%, and the content of (d2) is Y mass %, X> Y (Y ≠ 0), and (d) a photosensitive resin in which the total amount of the surfactant is 0.005% by mass or more and 0.10% by mass or less in the photosensitive resin composition It is a composition.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which is hard to produce external appearance defects, such as pin trace nonuniformity, a stripe unevenness, and a moyamura can be provided.

  The photosensitive resin composition of the present invention contains (a) a polyimide resin or a precursor thereof. Here, the polyimide resin refers to a resin having a cyclic structure such as an imide ring, an oxazole ring, an imidazole ring, and a thiazole ring in the main chain. Specific examples include polyimide, polybenzoxazole, polybenzimidazole, and polybenzothiazole. Examples of the precursors of these polyimide resins include polyamic acid, polyamic acid ester, which is a polyimide precursor, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, which are polybenzoxazole precursors. Among these, from the viewpoint of alkali developability, polyamic acid, polyamic acid ester, and polyhydroxyamide are preferable, and polyamic acid and polyamic acid ester are more preferable. In these resins, an imide ring is sufficiently formed even at a low temperature baking of 250 ° C. or lower, so that the chemical resistance in the low temperature baking is further improved.

  The polyimide resin preferably has a structural unit represented by the following general formula (1), and the precursor thereof preferably has a structural unit represented by the following general formula (2). Two or more kinds of resins having these structural units may be contained, or a copolymer of two or more kinds of structural units may be contained. The degree of polymerization of (a) the polyimide resin or its precursor in the present invention is preferably from 10 to 100,000.

In the general formula (1), R ¹ represents a C 4-30 tetravalent organic group. R ² represents a divalent to hexavalent organic group having 2 to 30 carbon atoms. E may be the same or different and represents OR ³ , SO ₃ R ³ , CONR ³ R ⁴ , COOR ³ or SO ₂ NR ³ R ⁴ . R ³ and R ⁴ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. X and Z represent CO, N, NH, O or S, and Y represents C or N. The bond between Z and Y is a single bond or a double bond. r and s represent an integer of 0 to 4. However, r + s> 0. q represents an integer of 0 to 2.

In the general formula (2), ^{R 5} and ^{R 6} represents a divalent to hexavalent organic group having 2 to 30 carbon atoms. A may be the same or different and represents OR ⁷ , SO ₃ R ⁷ , CONR ⁷ R ⁸ , COOR ⁷ or SO ₂ NR ⁷ R ⁸ . R ⁷ and R ⁸ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. m and p show the integer of 0-4. However, m + p> 0.

The resin having the structural unit represented by the general formula (1) represents a resin having a cyclic structure such as polyimide, polybenzoxazole, polybenzimidazole, and polybenzothiazole. R ^{1 in the} general formula (1) represents a tetravalent to octavalent organic group having 2 to 30 carbon atoms, and preferably has 1 to 2 aromatic rings. As a preferable structure of R ^{1 in} the general formula (1), the following structure and a part of these hydrogen atoms may be substituted with alkyl groups having 1 to 20 carbon atoms, fluoroalkyl groups, alkoxyl groups, ester groups, nitro groups, cyano groups. Examples thereof include a structure in which 1 to 4 groups are substituted with a group, a fluorine atom, or a chlorine atom.

In the general formula (1), R ² represents a 2 to 6-valent organic group having 2 to 30 carbon atoms, and preferably has 1 to 4 aromatic rings. As a preferable structure of R ^2- (E) _s of the general formula (1), the following structure and a part of these hydrogen atoms may be substituted with an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group, an alkoxyl group, or an ester group. , A nitro group, a cyano group, a fluorine atom, a structure substituted with 1 to 4 by a chlorine atom, and the like.

Where J is a direct bond, —COO—, —CONH—, —CH ₂ —, —C ₂ H ₄ —, —O—, —C ₃ H ₆ —, —SO ₂ —, —S—, —Si ( _{CH 3) 2 -, - O} -Si (CH 3) 2 -O -, - C 6 H 4 -, - C 6 H 4 -O-C 6 H 4 -, - C 6 H 4 -C 3 H 6 -C ₆ H ₄ - or _{-C 6 H 4 -C 3 F 6} -C 6 H 4 - shows a.

In General Formula (1), E represents OR ³ , SO ₃ R ³ , CONR ³ R ⁴ , COOR ^3, or SO ₂ NR ³ R ⁴ , and R ³ and R ⁴ are each a hydrogen atom or 1 to 10 carbon atoms. Valent hydrocarbon group. Among these, E is preferably a hydroxyl group, a carboxyl group, an ester group, a sulfonic acid group, a sulfonic acid amide group or a sulfonic acid ester group.

  In the general formula (1), X and Z represent CO, N, NH, O or S. Y is N or C, and when Y is C, one bond of XY or YZ becomes a double bond. q represents an integer of 0 to 2, and q = 0 is preferable.

In General Formula (2), R ⁵ represents a 2 to 6-valent organic group having 2 to 30 carbon atoms. Examples of the acid component constituting —CO—R ⁵ (A) _m —CO— in the general formula (2) include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, and bis (carboxyphenyl) hexafluoropropane. , Biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyl dicarboxylic acid, etc., as examples of tricarboxylic acid, trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid, etc., as examples of tetracarboxylic acid, pyromellitic acid, 3, 3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 2,2 ′, 3,3′-biphenyltetracarboxylic acid, 3,3 ′, 4 4′-benzophenone tetracarboxylic acid, 2,2 ′, 3,3′-benzopheno Tetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane, 1,1-bis (3,4- Dicarboxyphenyl) ethane, 1,1-bis (2,3-dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) methane, bis (2,3-dicarboxyphenyl) methane, bis (3 4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3, Aromatic tetracarboxylic acids such as 5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, butanetetracarboxylic acid, Examples thereof include aliphatic tetracarboxylic acids such as 1,2,3,4-cyclopentanetetracarboxylic acid. Among these, in tricarboxylic acid and tetracarboxylic acid, one or two carboxyl groups correspond to the A group in the general formula (2). In addition, 1 to 4 dicarboxylic acids, tricarboxylic acids, and tetracarboxylic acids exemplified above are substituted with the A group in the general formula (2), preferably a hydroxyl group, a sulfonic acid group, a sulfonic acid amide group, a sulfonic acid ester group, or the like. Is more preferable. These acids can be used as they are, or as acid anhydrides and active esters. Two or more of these may be used.

R ^{6 in the} general formula (2) represents a divalent to hexavalent organic group having 2 to 30 carbon atoms, and preferably has an aromatic ring and / or an aliphatic ring. Examples of the diamine component constituting —NH—R ⁶ (A) _p —NH— in the general formula (2) include bis (3-amino-4-hydroxyphenyl) hexafluoropropane and bis (3-amino-4-hydroxy). Phenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4) -Hydroxy) biphenyl, hydroxyl group-containing diamine such as bis (3-amino-4-hydroxyphenyl) fluorene, carboxyl group-containing diamine such as 3,5-diaminobenzoic acid, 3-carboxy-4,4'-diaminodiphenyl ether, Sulfonic acid-containing diesters such as 3-sulfonic acid-4,4′-diaminodiphenyl ether Min, dithiohydroxyphenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4, 4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy) benzene, benzine, m-phenylenediamine, p-phenylene Diamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- ( 4-Aminophenoxy) phenyl } Ether, 1,4-bis (4-aminophenoxy) benzene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-diethyl-4,4′-diaminobiphenyl, 3,3 ′ -Dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2 ', 3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3 ', 4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di (trifluoromethyl) -4,4'-diaminobiphenyl, or at least one of the hydrogen atoms of these aromatic rings Examples thereof include compounds in which a part is substituted with a monovalent hydrocarbon group having 1 to 10 carbon atoms such as an alkyl group, a fluoroalkyl group having 1 to 10 carbon atoms, or a halogen atom. Moreover, aliphatic cyclohexyl diamine, methylene bis cyclohexyl amine, etc. are also mentioned. However, in applications where heat resistance is required, it is preferable to use an aromatic diamine in an amount of 50 mol% or more of the total diamine. These diamines can be used as diamines or as corresponding diisocyanate compounds, trimethylsilylated diamines. Two or more of these may be used.

In the general formula (2), A represents OR ⁷ , SO ₃ R ⁷ , CONR ⁷ R ⁸ , COOR ⁷ or SO 2 NR ⁷ R ⁸ , wherein R ⁷ and R ⁸ are a hydrogen atom or a monovalent having 1 to 20 carbon atoms. A hydrocarbon group is shown. Of these, A is preferably a hydroxyl group.

  As an acid dianhydride component of the resin having the structural unit represented by the general formula (1) or (2), a silicon atom such as dimethylsilanediphthalic acid or 1,3-bis (phthalic acid) tetramethyldisiloxane Copolymerization of the dianhydride of the tetracarboxylic acid containing 1 to 30 mol% of the total acid dianhydride component, or 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3 as the diamine component It is preferable to copolymerize 1-30 mol% of all diamine components with a silicon atom-containing diamine such as bis (4-anilino) tetramethyldisiloxane. By having these residues, the adhesiveness of the resulting photosensitive resin composition to the substrate can be enhanced, and the resistance to oxygen plasma and UV ozone treatment used for cleaning and the like can be enhanced.

  Polyimide can be obtained by reacting tetracarboxylic acid, corresponding tetracarboxylic dianhydride, tetracarboxylic diester dichloride and the like with diamine, corresponding diisocyanate compound, and trimethylsilylated diamine. It is common to react a tetracarboxylic dianhydride and a diamine to obtain a polyamic acid, which is one of polyimide precursors, and to obtain a polyimide by dehydration and ring closure by heating or chemical treatment such as acid or base. . In the present invention, polyamic acid ester, polyamic acid amide, polyisoimide and the like which are polyimide precursors can be used in addition to polyimide and polyamic acid.

  Polybenzoxazole can be obtained by reacting bisaminophenol with dicarboxylic acid, the corresponding dicarboxylic acid chloride, dicarboxylic acid active ester and the like. A polyhydroxyamide, which is one of the polybenzoxazole precursors, is obtained by reacting a bisaminophenol compound with a dicarboxylic acid, and dehydrated and closed by heating or chemical treatment of phosphoric anhydride, base, carbodiimide compound, etc. It is common to obtain oxazoles.

  Polybenzothiazole can be obtained by reacting bisaminothiophenol with dicarboxylic acid, the corresponding dicarboxylic acid chloride, dicarboxylic acid active ester and the like. By reacting a bisaminothiophenol compound with a dicarboxylic acid, polythiohydroxyamide, which is one of the polybenzothiazole precursors, is obtained. It is common to obtain benzothiazole.

  Polybenzimidazole can be obtained by reacting tetraamine with dicarboxylic acid, the corresponding dicarboxylic acid chloride, dicarboxylic acid active ester and the like. A polyaminoamide, which is one of the polybenzimidazole precursors, is obtained by reacting a bisaminophenol compound and a dicarboxylic acid, and polybenzimidazole is dehydrated and closed by heating or chemical treatment of phosphoric anhydride, base, carbodiimide compound, etc. It is common to get

  In addition, the ends of these polyimide resins or their precursors are sealed with a terminal sealing agent such as a monoamine, acid anhydride, acid chloride, or monocarboxylic acid having a hydroxyl group, carboxyl group, sulfonic acid group, or thiol group. It is preferable that the dissolution rate of the resin in the alkaline aqueous solution can be adjusted to a preferable range.

  Examples of monoamines include 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene. 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy- 5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-amino Salicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2 -Aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. are mentioned. Two or more of these may be used.

  Examples of acid anhydrides, acid chlorides and monocarboxylic acids include phthalic anhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylic anhydride, acid anhydrides such as 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7- Monocarboxylic acids such as carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid and the carboxyl groups thereof are converted to acid chlorides. Mono acid chloride compounds, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, etc. Monoacid chloride compound in which only one carboxyl group of dicarboxylic acids of the above is acid chloride, obtained by reaction of monoacid chloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide Active ester compounds that can be used. Two or more of these may be used.

The end-capping agent introduced into the resin can be easily detected by the following method. For example, by dissolving the resin into which the end-capping agent has been introduced in an acidic solution and decomposing it into an amine component and an acid anhydride component that are the structural units of the resin, this is measured by gas chromatography (GC) or NMR measurement, The end capping agent can be easily detected. Apart from this, it is possible to directly detect the resin into which the end-capping agent has been introduced by pyrolysis gas chromatograph (PGC), infrared spectrum and ¹³ C NMR spectrum measurement.

  The photosensitive resin composition of the present invention contains (b) a quinonediazide compound. (B) Since the photosensitive resin composition obtained by containing a quinonediazide compound has positive photosensitivity, the radiation effective intensity to the inside of the coating film of an exposed part is from the surface of a coating film in pattern processing. An insulating layer that gradually becomes smaller toward the bottom and has a gentle forward tapered cross-sectional shape can be easily formed.

  As the quinonediazide compound, a compound in which naphthoquinonediazidesulfonic acid is ester-bonded to a compound having a phenolic hydroxyl group is more preferable. As the compound having a phenolic hydroxyl group used here, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-PHBA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP -IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-p-CR, Methylenetetra-p-CR, BisRS-26X, Bis-PFP-PC Manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A ( Above, trade name, manufactured by Asahi Organic Materials Co., Ltd.), naphthol, Tet Hydroxybenzophenone, methyl gallate, bisphenol A, methylenebisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co.) and the like are preferable. As the naphthoquinone diazide sulfonic acid, 4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid is preferable. Such a naphthoquinonediazide compound has high photosensitivity with respect to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp. The molecular weight of the naphthoquinone diazide compound is preferably 300 to 1000 from the viewpoint of thermal decomposability in heat treatment. The content of (b) naphthoquinonediazide compound is preferably 1 to 50 parts by mass with respect to 100 parts by mass of (a) polyimide resin or its precursor.

  If necessary, the compound having a phenolic hydroxyl group may be contained as it is without esterification with naphthoquinonediazide. By containing this compound having a phenolic hydroxyl group, the resulting photosensitive resin composition hardly dissolves in an alkali developer before exposure, and easily dissolves in an alkali developer upon exposure. There is little decrease, and development is easy in a short time. In this case, the content of the compound having a phenolic hydroxyl group is preferably 3 to 40 parts by mass with respect to (a) 100 parts by mass of the polyimide resin or its precursor.

  The photosensitive resin composition of the present invention may further contain a compound that generates an acid upon irradiation with ultraviolet rays or actinic radiation. Examples of such compounds include onium salts, halogen-containing compounds, diazoketone compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and sulfonimide compounds. Two or more of these may be contained. These contents are preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the (a) polyimide resin or its precursor.

  The photosensitive resin composition of the present invention may further contain a thermal crosslinking agent. As the thermal crosslinking agent, an alkoxymethyl group-containing compound represented by the following general formula (3) is preferable.

In the general formula (3), ^{R 9} represents a hydrocarbon group having 1 to 6 carbon ^{atoms, R 10} is _CH 2 ^{OR 30 (R} 30 is a hydrogen atom or an organic group having 1 to 6 carbon atoms). R ³⁰ is preferably a hydrocarbon group having 1 to 4 carbon atoms, particularly a methyl group or an ethyl group, because it retains moderate reactivity and is stable. R ¹¹ represents a hydrogen atom, a methyl group or an ethyl group, and R ^{12 to} R ²⁹ represent a hydrogen atom, an organic group having 1 to 20 carbon atoms, Cl, Br, I or F. u represents an integer of 2 to 4, and 3 or 4 is more preferable. When u is 3 or more, the crosslink density of the cured film is increased and the chemical resistance is further improved, which is preferable.

  The alkoxymethyl group-containing compound represented by the general formula (3) has a higher cross-linking reaction temperature and higher cross-linking reactivity than the urea / melamine-based heat cross-linking agent, so that the cross-linking reaction in the pre-bake process during pattern processing Can be prevented, and the chemical resistance of the resulting cured film can be improved. In particular, even when baked at a low temperature of 250 ° C. or lower, a cured film having sufficient chemical resistance can be obtained. Moreover, since the crosslinking reaction in a prebaking process can be prevented, when it is set as the photosensitive resin composition, it has a high sensitivity at the time of pattern processing. The purity of the compound represented by the general formula (3) is preferably 80% or more, and more preferably 95% or more. If the purity is 80% or more, the crosslinking reaction of the photosensitive resin composition can be sufficiently performed to reduce the number of unreacted groups that become the water-absorbing groups, so that the water absorption of the photosensitive resin composition can be reduced. Can do. Examples of a method for obtaining a high-purity thermal crosslinking agent include a method of collecting only the desired product by performing recrystallization, distillation or the like. The purity of the thermal crosslinking agent can be determined by a liquid chromatography method.

  An example of the compound preferably used in the present invention as the thermal crosslinking agent represented by the general formula (3) is shown below.

  From the viewpoint of chemical resistance, the content of the thermal crosslinking agent is preferably 10 parts by mass or more, more preferably 20 parts by mass or more with respect to 100 parts by mass of (a) the polyimide resin or its precursor. Moreover, 100 mass parts or less are preferable from a viewpoint of the stability of the photosensitive resin composition and the water absorption rate of a coating film, and 80 mass parts or less are more preferable.

  The photosensitive resin composition of the present invention contains (c) a solvent. (C) As a solvent, the organic solvent whose boiling point under atmospheric pressure is 100 degreeC or more and 250 degrees C or less is preferable. By containing an organic solvent having a boiling point in this range, striation associated with drying during spin coating can be suppressed, and the solvent can be easily removed. In particular, by setting the boiling point to 100 ° C. or higher, the evaporation of the solvent becomes an appropriate range when the photosensitive resin composition is applied by the slit coat method. In addition, (a) since the polyimide resin or its precursor is appropriately dissolved, it is possible to suppress the precipitation of solids in the coating die and the generation of foreign matter, and to prevent the occurrence of uneven stripes (streaky thickness unevenness) in the coating film. Can be suppressed. In the present invention, from the viewpoint of applicability of the photosensitive resin composition, it is preferable to contain at least one solvent having a boiling point of 100 ° C. or more and less than 140 ° C. and at least one solvent having a boiling point of 140 ° C. or more and 250 ° C. or less. It is preferable to contain a material having a temperature of 100 ° C. or more and less than 140 ° C. of 50% by mass or more and 95% by mass or less with respect to the total solvent, and a material having a temperature of 140 ° C. or more and 250 ° C. or less of . By containing a solvent having a boiling point of 100 ° C. or more and less than 140 ° C. with respect to the total solvent of 50% by mass or more and 95% by mass or less, traces of pins and suction chucks are hardly generated in the coating film drying process, and rinsing is performed in the edge back rinsing process It is possible to suppress such a phenomenon that the liquid penetrates the coating film and the edge is not cut cleanly. Occurs when vacuum drying is used in the coating film drying step after application of the photosensitive resin composition by containing a solvent having a boiling point of 140 ° C. or more and 250 ° C. or less with respect to all the solvents in an amount of 5% by mass to 50% by mass. It is possible to suppress the occurrence of coating film unevenness and pin mark unevenness, which is called Benard cell (a pattern derived from convection that occurs when the solvent volatilizes from the coating film surface). Further, when the content of the solvent at 140 ° C. or more and 250 ° C. or less is 50% by mass or less, the amount of the residual solvent in the prebaked film can be reduced, and the film loss during development can be reduced.

  Examples of the organic solvent having a boiling point of 100 ° C. or higher and lower than 140 ° C. include alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propyl acetate, butyl acetate, Alkyl acetates such as isobutyl acetate, ketones such as acetylacetone, methylpropylketone, methylbutylketone, methylisobutylketone, cyclopentanone, alcohols such as butylalcohol, isobutylalcohol, pentanol, 4-methyl-2-pentanol And aromatic hydrocarbons such as toluene and xylene. Two or more of these may be contained. Among these, propylene glycol monomethyl ether or propylene glycol monoethyl ether is preferable.

  As the organic solvent having a boiling point of 140 ° C. or more and 250 ° C. or less, a polar solvent is preferable, and N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl Examples thereof include sulfoxide, γ-butyrolactone, 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate, diacetone alcohol, ethyl lactate, and butyl lactate. Two or more of these may be contained.

  On the other hand, a solvent having a boiling point of less than 100 ° C. is not preferable because the coating property deteriorates when applied by the slit coating method, but it may be in the range of 0% by mass to 30% by mass with respect to the total amount of the organic solvent. Can be contained.

  The photosensitive resin composition of the present invention contains (d) a surfactant. The surfactant contains (d1) a silicon-based surfactant and (d2) a surfactant having a fluorine atom, (d) the content of (d1) in the photosensitive resin composition is X mass%, (d2) When X content is Y mass%, X> Y (Y ≠ 0) and (d) the total amount of the surfactant is 0.005 mass% or more and 0.10 mass% in the photosensitive resin composition. It is characterized by the following. (D1) The silicon-based surfactant has an effect of suppressing defects such as stripe unevenness and improving coating characteristics. In addition, (d2) a surfactant having a fluorine atom has an effect of suppressing the occurrence of pin mark unevenness and moire unevenness. Here, (d1) silicon-based surfactant in the present invention refers to one having a siloxane bond. In addition, the silicon-based surfactant having a fluorine atom is classified as (d2).

  In the present invention, when the content of (d1) silicon-based surfactant in the photosensitive resin composition is X mass% and (d2) the content of the surfactant having a fluorine atom is Y mass%, X> Y It is important that (Y ≠ 0). When X ≦ Y, receding unevenness increases from the edge of the substrate during application of the photosensitive resin composition, thickness uniformity decreases, and a large amount of unevenness occurs. Further, (d) the total amount of the surfactant needs to be 0.005 mass% (50 ppm) or more and 0.10 mass% (1000 ppm) or less in the photosensitive resin composition. 100 ppm or more is preferable from the viewpoint of further improving applicability. Moreover, 600 ppm or less is preferable from a viewpoint of improving compatibility with the photosensitive resin composition, further improving the in-plane uniformity of the coating film, and suppressing unevenness.

  In the present invention, (d) the total amount of the surfactant, (d1) the content of the silicon-based surfactant, and (d2) the content of the surfactant having a fluorine atom are within the above ranges, thereby forming a photosensitive resin composition. It is possible to suppress the occurrence of pin mark unevenness, haze unevenness, receding unevenness, and non-uniformity seen during application of an object, and to form a coating film with less unevenness. The content of the (d1) silicon surfactant in the photosensitive resin composition is preferably 40 ppm or more and 800 ppm or less, and more preferably 80 ppm or more and 500 ppm or less. In addition, the content of the surfactant (d2) having a fluorine atom in the photosensitive resin composition is preferably more than 0 ppm and less than 500 ppm, more preferably more than 50 ppm and less than 300 ppm.

  (D1) Specific examples of silicon-based surfactants include SH series, SD series, ST series from Toray Dow Corning Silicone, BYK series from Big Chemie Japan, KP series from Shin-Etsu Silicone, Japan Examples include, but are not limited to, the Oil series Disperse Series and Toshiba Silicone TSF Series.

  (D2) Examples of the surfactant having a fluorine atom include a surfactant having a fluorocarbon chain. Specifically, Dainippon Ink & Co., Ltd.'s "MegaFac (registered trademark)" series, Sumitomo 3M's Florad series, Asahi Glass's "Surflon (registered trademark)" series, "Asahi Guard (registered trademark)" series And EF series of Shin-Akita Kasei Co., Ltd., but are not limited thereto.

  The photosensitive resin composition of the present invention preferably contains a silane coupling agent such as trimethoxyaminopropylsilane, trimethoxyepoxysilane, trimethoxyvinylsilane, trimethoxythiolpropylsilane. By containing these, adhesion to the substrate can be enhanced, and resistance to oxygen plasma and UV ozone treatment used for cleaning and the like can be enhanced.

  Moreover, as for the solid content concentration of the photosensitive resin composition of this invention, 5 mass% or more and 20 mass% or less are preferable. If the solid content concentration is 5% by mass or more, the formation of a thick film is easy, and if the solid content concentration is 20% by mass or less, a highly uniform coating film can be easily obtained.

  The manufacturing method of the photosensitive resin composition of this invention is illustrated. For example, (a) to (d) components, and if necessary, other components in a glass flask or stainless steel container and stirred and dissolved with a mechanical stirrer, etc., ultrasonically dissolved, planetary stirring and defoaming The method of stirring and dissolving with an apparatus is mentioned. Moreover, you may filter with a filter of the pore size of 0.05 micrometer-5 micrometers in order to remove a foreign material.

  Next, a method for forming a heat resistant resin film using the photosensitive resin composition of the present invention will be described with examples.

First, a photosensitive resin composition is applied on a substrate to form a photosensitive resin film. Examples of the material of the substrate include all materials that can be provided with the electrode metal on the surface, such as metal, glass, semiconductor, metal oxide insulating film, silicon nitride, polymer film such as polyethylene terephthalate and polyethersulfone. Glass is preferred. The material of the glass is not particularly limited, but alkali zinc borosilicate glass, sodium borosilicate glass, soda lime glass, low alkali borosilicate glass, barium borosilicate glass, borosilicate glass, aluminosilicate glass, fused quartz glass And synthetic quartz glass. Usually, soda-lime glass with a barrier coating such as non-alkali glass or SiO ₂ with few ions eluted from the glass is used. The thickness of the substrate only needs to be sufficient to maintain mechanical strength. If the material is inorganic, it is 0.1 mm or more, preferably 0.5 mm or more, and if the material is organic, 0.05 mm or more, Preferably it is 0.1 mm or more. The size of the substrate is not particularly limited, but a rectangular or square rectangular substrate having a side of 150 mm or more and a round substrate can provide a good coating film on a substrate having a diameter of 6 inches or more.

  Examples of the coating method include slit coating, spin coating, spray coating, roll coating, and bar coating. Two or more of these techniques may be combined. The photosensitive resin composition of the present invention is most effective in the slit coat method. The slit coating method can be applied with a small amount of coating liquid, and is advantageous for cost reduction. The amount of coating liquid required for the slit coating method is, for example, about 1/5 to 1/10 as compared with the spin coating method. On the other hand, the slit coating method has a problem that defects such as pin mark unevenness and streaking are likely to occur. However, if the photosensitive resin composition of the present invention is used, defects such as pin mark unevenness and streaking can be suppressed even when applied using a slit coating method.

  Moreover, although a coating film thickness changes with application methods, solid content concentration of a photosensitive resin composition, a viscosity, etc., the film thickness after drying is usually 0.1 to 100 μm, preferably 0.3 to 20 μm. To be applied.

  Next, the photosensitive resin film is dried under reduced pressure to remove the solvent. The vacuum ultimate pressure is preferably 20 to 150 Pa, and the drying time is preferably 10 to 100 seconds.

  It is preferable to provide a step of heating the photosensitive resin film dried under reduced pressure using a hot plate, oven, infrared ray, vacuum chamber or the like. This process is also called pre-baking. When using a hot plate, a substrate provided with a photosensitive resin film is held and heated directly on the plate or on a jig such as a proxy pin installed on the plate. Examples of the material of the proxy pin include a metal material such as aluminum and stainless steel, or a synthetic resin such as polyimide resin and “Teflon (registered trademark)”, and any proxy pin may be used. The height of the proxy pin varies depending on the size of the substrate, the type of the photosensitive resin film, the purpose of heating, and the like. For example, the photosensitive resin film applied on a 400 mm × 500 mm × 0.7 mm glass substrate is heated. In this case, the height of the proxy pin is preferably about 2 to 12 mm. The heating temperature varies depending on the type and purpose of the photosensitive resin film, and it is preferably performed in the range of room temperature to 180 ° C. for 1 minute to several hours.

  Next, the photosensitive resin composition film is exposed to actinic radiation through a mask having a desired pattern. As the actinic radiation used for exposure, there are ultraviolet rays, visible rays, electron beams, X-rays and the like. In the present invention, it is preferable to use i rays (365 nm), h rays (405 nm), and g rays (436 nm) of a mercury lamp. .

  After the exposure, a resin film having a desired pattern is formed by developing to remove the exposed portion using a developer. Developers include tetramethylammonium aqueous solution, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethyl An aqueous solution of a compound showing alkalinity such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable. In addition, polar solutions such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, isopropanol, etc. Alcohols, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added singly or in combination. After development, it is preferable to perform a rinsing treatment with water. Here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.

  After development, heat treatment is performed to convert the photosensitive resin film into a heat-resistant resin film. This process is also called post-bake. The heating temperature is preferably 130 to 500 ° C., and it is preferably heated for 5 minutes to 5 hours while raising the temperature stepwise or continuously. As an example, there is a method of performing heat treatment at 130 ° C., 200 ° C., and 350 ° C. for 30 minutes each. Further, a method of linearly raising the temperature from room temperature to 250 ° C. over 2 hours or from room temperature to 400 ° C. over 2 hours can be mentioned.

  The heat-resistant resin film formed from the photosensitive resin composition of the present invention is suitable for applications such as semiconductor passivation films, surface protective films or interlayer insulating films of electronic components such as semiconductor elements, and insulating layers of organic electroluminescent elements. Used.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited by these examples. In addition, evaluation of the photosensitive resin composition in an Example was performed with the following method.

<Method for producing photosensitive resin film>
A glass substrate in which an ITO transparent electrode film having a thickness of 125 nm is formed on the surface of a non-alkali glass (# 1737 manufactured by Corning Japan Co., Ltd., # 1737) having a size of 400 mm × 500 mm × 0.7 mm and 200 mm × 214 mm × 0.7 mm. Prepared. A photoresist was applied onto the ITO film by a spinner, and patterning was performed by exposure and development by a normal photolithography method. After removing unnecessary portions of ITO by etching, the photoresist was removed to pattern the ITO film into a stripe shape having a length of 90 mm, a width of 80 μm, and a pitch of 100 μm. This striped ITO film becomes the first electrode when an organic electroluminescent device is formed.

  A photosensitive resin composition (hereinafter referred to as varnish) was applied onto a glass substrate patterned with ITO so that the film thickness after drying was 1.5 μm. The application onto the 400 mm × 500 mm substrate was performed by slit coating, the nozzle scan speed was 4 m / min, and the nozzle-substrate gap was 150 μm. Application onto a 200 mm × 214 mm substrate was performed by spin coating, the amount of varnish dropped onto the center of the substrate was 20 g, and the rotation speed was 600 rpm for 30 seconds.

Next, the substrate was dried under reduced pressure. The solvent was removed by drying under reduced pressure for 60 seconds at an ultimate pressure of 60 Pa. Thereafter, using a hot plate (EA-4331 manufactured by Chuo Riken Co., Ltd.), the glass substrate is held at a height of 25.0 mm from the hot plate with a proxy pin, heated at 120 ° C. for 10 minutes, and dried. A functional resin film was obtained. Since the distance between the top plate and the hot plate in the decompression chamber was 30.0 mm, the distance between the glass substrate and the top plate was about 5 mm. Proxy pin diameter D = 2.0 mm, the cross-sectional area S1 = 3.1 mm ^2, the contact area S2 = 0.5 mm ² of the glass substrate, and a height of = 10 mm. The material used was “SUS304A”, which is a stainless material.

<Evaluation method of photosensitive resin film>
The surface of the photosensitive resin film formed by the slit coating method described above was observed under sodium lamp irradiation, and the applicability, pin mark unevenness, streak unevenness, horizontal dan, moy unevenness, and presence / absence of receding were visually evaluated. Further, the surface of the photosensitive resin film formed by the spin coating method was observed under irradiation of a sodium lamp, and visually evaluated for applicability, pin mark unevenness, striation, and moire unevenness. The evaluation result was expressed by a five-level evaluation, and a very good one was judged as 5, a good one as 4, a normal one as 3, a bad one as 2, and a very bad one as 1.

Synthesis Example 1 Synthesis of hydroxyl group-containing diamine compound 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (manufactured by Central Glass Co., Ltd., BAHF) in 100 mL of acetone , 17.4 g (0.3 mol) of propylene oxide (Tokyo Kasei Co., Ltd.), and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of acetone was added dropwise thereto. After completion of dropping, the mixture was stirred at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.
30 g of the obtained white solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated by confirming that the balloons did not squeeze any more. After completion of the reaction, the catalyst was filtered to remove the palladium compound as a catalyst, and the mixture was concentrated with a rotary evaporator to obtain a hydroxyl group-containing diamine compound represented by the following formula.

Synthesis Example 2 Synthesis of quinonediazide compound TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 21.22 g (0.05 mol) and 5-naphthoquinonediazidesulfonic acid chloride (Toyo Gosei Co., Ltd.) under a dry nitrogen stream ), NAC-5) 26.8 g (0.1 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 12.65 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system would not be 35 ° C. or higher. After dropping, the mixture was stirred at 40 ° C. for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration and further washed with 1 L of 1% aqueous hydrochloric acid. Thereafter, it was further washed twice with 2 L of water. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound represented by the following formula.

Synthesis Example 3 Synthesis of Alkali-Soluble Resin A1 In a 200 ml four-necked flask equipped with a stirrer, a condenser tube and a thermometer, 6.8 g of methacrylic acid, 14.2 g of N-cyclohexylmaleimide, 3-ethyl-3-methacryloxy 17.8 g of methyl octacene, 45.3 g of ethyl 3-ethoxypropionate, 45.3 g of diethynyl glycol methyl ethyl ether, and 1.1 g of azobisisobutyronitrile were added. This four-necked flask was immersed in an oil bath, the temperature in the flask was maintained at 100 to 110 ° C., and stirred for 3 hours in a nitrogen atmosphere to react to obtain an alkali-soluble resin A1.

Synthesis Example 4 Synthesis of Silicone Surfactant Compound represented by the following chemical formula (4) in the flask, that is, 204 g of polyoxyethylene having an allyl group and an OH group at the molecular chain end, 300 g of isopropyl alcohol, 2 mass of chloroplatinic acid A 0.5% isopropyl alcohol solution and 1 g of potassium acetate were added and mixed. Next, after raising the temperature to the reflux temperature of isopropyl alcohol (83 ° C.), 111 g of methylsiloxane represented by the following chemical formula (5) was gradually added dropwise to cause addition reaction.

  After completion of the dropwise addition, the reaction was further continued for 4 hours, and the reaction was terminated after confirming the formation of SiH groups. Next, isopropyl alcohol was removed by heating at 110 ° C./1.3 kPa for 2 hours to obtain 310 g of a compound represented by the following chemical formula (6).

Synthesis Example 5 Synthesis of Polyamide A2 443.2 g of dicarboxylic acid derivative obtained by reacting 1 mol of diphenyl ether-4,4′-dicarboxylic acid with 2 mol of 1-hydroxy-1,2,3-benzotriazole (0. 9 mol) and 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (manufactured by Central Glass Co., Ltd., BAHF) 366.3 g (1.0 mol) were added to a thermometer, a stirrer, and raw materials. The flask was put into a four-necked separable flask equipped with a dry nitrogen gas inlet tube, and 3000 g of N-methyl-2-pyrrolidone (NMP) was added and dissolved. Thereafter, the mixture was reacted at 75 ° C. for 12 hours using an oil bath. Next, 32.8 g (0.2 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 500 g of NMP was added, and the mixture was further stirred for 12 hours to complete the reaction. The reaction mixture was filtered, and then poured into a mixed solution of water / methanol = 3/1. The precipitate was collected by filtration, sufficiently filtered with water, and then dried under vacuum to obtain polyamide A2.

Example 1
Under a dry nitrogen stream, 57.4 g (0.095 mol) of the hydroxyl group-containing diamine obtained in Synthesis Example 1 and 1.24 g (0.005 mol) of bisaminopropyltetramethyldisiloxane were dissolved in 200 g of NMP. Oxydiphthalic dianhydride 31.0g (manac Co., Ltd. make, 0.1 mol) was added here, and it stirred at 40 degreeC for 2 hours. Thereafter, a solution obtained by diluting 7.14 g (0.06 mol) of dimethylformamide dimethyl acetal (manufactured by Mitsubishi Rayon Co., Ltd., DFA) with 5 g of NMP was added dropwise over 10 minutes. After dropping, stirring was continued at 40 ° C. for 2 hours. After the completion of stirring, the solution was poured into 2 L of water, and a precipitate of polymer solid was collected by filtration. Further, it was washed with 2 L of water three times, and the collected polymer solid was dried with a vacuum dryer at 50 ° C. for 72 hours to obtain polyamic acid.

  10 g of the polyamic acid thus obtained and 1.8 g of the quinonediazide compound obtained in Synthesis Example 2 are dissolved in a mixed solvent of 55 g of propylene glycol monomethyl ether, 18 g of γ-butyrolactone and 18 g of ethyl lactate, and a photosensitive polyimide precursor is obtained. A composition was prepared. Thereto, 290 ppm of a silicon surfactant TSF400 (manufactured by Toshiba Silicone Co., Ltd.) and 175 ppm of a surfactant Ftop EF301 (manufactured by Shin-Akita Kasei Co., Ltd.) having a fluorine atom are added to the resin composition. Thus, a varnish W1 of a photosensitive polyimide precursor composition was obtained. A photosensitive resin film was produced by the above-described method using the obtained varnish W1, and the evaluation results are shown in Table 2.

Example 2
Silicone surfactant TSF400 (manufactured by Toshiba Silicone Co., Ltd.) 290 ppm, BYK-333 (manufactured by Big Chemie Co., Ltd.) 320 ppm, fluorine-containing surfactant F-top EF301 (manufactured by Shin-Akita Kasei Co., Ltd.) 175 ppm Instead, a varnish W2 of a photosensitive polyimide precursor composition was obtained in the same manner as in Example 1 except that 80 ppm of “Megafac” F-475 (manufactured by Dainippon Ink Industries, Ltd.) was used. The results of evaluation in the same manner as in Example 1 using the obtained varnish W2 are shown in Table 2.

Example 3
Silicone surfactant TSF400 (manufactured by Toshiba Silicone Co., Ltd.) 290 ppm, SF8410 (polyether-modified silicone oil, Toray Dow Corning Silicone Co., Ltd.) 540 ppm, fluorine-containing surfactant F-top EF301 (Shin-Akita) A varnish W3 of a photosensitive polyimide precursor composition was obtained in the same manner as in Example 1 except that 60 ppm of "Megafac" BL20 (manufactured by Dainippon Ink Industries, Ltd.) was used instead of 175 ppm. It was. The results of evaluation in the same manner as in Example 1 using the obtained varnish W3 are shown in Table 2.

Example 4
Silicone surfactant TSF400 (manufactured by Toshiba Silicone Co., Ltd.) 290 ppm, KP321 (manufactured by Shin-Etsu Silicone Co., Ltd.) 220 ppm, fluorine-containing surfactant F top EF301 (manufactured by Shin-Akita Kasei Co., Ltd.) 175 ppm Instead, “Asahi Guard” AG-7000 (Asahi Glass Co., Ltd.) 180 ppm was used in the same manner as in Example 1 to obtain a photosensitive polyimide precursor composition varnish W4. The results of evaluation in the same manner as in Example 1 using the obtained varnish W4 are shown in Table 2.

Example 5
Silicon surfactant TSF400 (manufactured by Toshiba Silicone Co., Ltd.) 290 ppm instead of SH8400 (manufactured by Toray Dow Corning Silicone Co., Ltd.) 30 ppm, surfactant F-top EF301 having fluorine atoms (manufactured by Shin-Akita Kasei Co., Ltd.) Varnish W5 of a photosensitive polyimide precursor composition was obtained in the same manner as in Example 1 except that 25 ppm of FC-170C (manufactured by Sumitomo 3M Limited) was used instead of 175 ppm. The results of evaluation in the same manner as in Example 1 using the obtained varnish W5 are shown in Table 2.

Example 6
Example 5 except that 30 ppm of silicon surfactant SH8400 (manufactured by Toray Dow Corning Silicone Co., Ltd.) was changed to 70 ppm and surfactant FC-170C having a fluorine atom (manufactured by Sumitomo 3M Ltd.) 25 ppm was changed to 40 ppm. The varnish W6 of the photosensitive polyimide precursor composition was obtained in the same manner. The results of evaluation in the same manner as in Example 1 using the obtained varnish W6 are shown in Table 2.

Example 7
Example 5 except that 30 ppm of silicon surfactant SH8400 (manufactured by Toray Dow Corning Silicone Co., Ltd.) was changed to 400 ppm, and surfactant FC-170C having a fluorine atom (manufactured by Sumitomo 3M Ltd.) 25 ppm was changed to 160 ppm. The varnish W7 of the photosensitive polyimide precursor composition was obtained in the same manner. The results of evaluation in the same manner as in Example 1 using the obtained varnish W7 are shown in Table 2.

Example 8
Example 5 except that silicon surfactant SH8400 (Toray Dow Corning Silicone Co., Ltd.) 30 ppm was changed to 550 ppm, and surfactant FC-170C having a fluorine atom (Sumitomo 3M Co., Ltd.) 25 ppm was changed to 450 ppm. The varnish W8 of the photosensitive polyimide precursor composition was obtained in the same manner. Table 2 shows the results of evaluation in the same manner as in Example 1 using the obtained varnish W8.

Comparative Example 1
Example 5 except that silicon surfactant SH8400 (manufactured by Toray Dow Corning Silicone Co., Ltd.) 30 ppm was changed to 1600 ppm and surfactant FC-170C (manufactured by Sumitomo 3M Co., Ltd.) 25 ppm was changed to 640 ppm. The varnish W9 of the photosensitive polyimide precursor composition was obtained in the same manner. Table 2 shows the results of evaluation in the same manner as in Example 1 using the obtained varnish W9.

Comparative Example 2
Varnish W10 of the photosensitive polyimide precursor composition was obtained like Example 5 except not having added silicon type surfactant and surfactant containing a fluorine atom. Table 2 shows the results of evaluation in the same manner as in Example 1 using the obtained varnish W10.

Comparative Example 3
Photosensitive polyimide precursor composition in the same manner as in Example 5 except that silicon surfactant SH8400 (manufactured by Toray Dow Corning Silicone Co., Ltd.) 30 ppm was changed to 400 ppm and no surfactant having a fluorine atom was added. Varnish W11 was obtained. The results of evaluation in the same manner as in Example 1 using the obtained varnish W11 are shown in Table 2.

Comparative Example 4
A photosensitive polyimide precursor composition was prepared in the same manner as in Example 5 except that no fluorine-based surfactant FC-170C (manufactured by Sumitomo 3M Co., Ltd.) 25 ppm was changed to 450 ppm. Varnish W12 was obtained. The results of evaluation in the same manner as in Example 1 using the obtained varnish W12 are shown in Table 2.

Comparative Example 5
Example 5 except that silicon surfactant SH8400 (manufactured by Toray Dow Corning Silicone Co., Ltd.) 30 ppm was changed to 400 ppm and surfactant FC-170C having a fluorine atom (manufactured by Sumitomo 3M Co., Ltd.) 25 ppm was changed to 450 ppm. The varnish W13 of the photosensitive polyimide precursor composition was obtained in the same manner as above. Table 2 shows the results of evaluation in the same manner as in Example 1 using the obtained varnish W13.

Comparative Example 6
Photosensitivity by dissolving 10 g of the polyamic acid obtained in Example 1, 1.5 g of the quinonediazide compound obtained in Synthesis Example 2, and 0.3 g of vinylmethoxysilane in a mixed solvent of 25 g of propylene glycol monomethyl ether and 25 g of γ-butyrolactone. The varnish W14 of the conductive polyimide precursor composition was obtained. The results of evaluation in the same manner as in Example 1 using the obtained varnish W14 are shown in Table 2.

Comparative Example 7
10 g of the polyamic acid obtained in Example 1 and 2.9 g of the quinonediazide compound obtained in Synthesis Example 2 were dissolved in 100 g of ethyl lactate to prepare a photosensitive polyimide precursor composition. Thereto, 2600 ppm of a surfactant Megafac BL20 (produced by Dainippon Ink & Chemicals, Inc.) having a fluorine atom was added to obtain a varnish W15 of a photosensitive polyimide precursor composition. The results of evaluation in the same manner as in Example 1 using the obtained varnish W15 are shown in Table 2.

Comparative Example 8
The same as in Example 1 except that 290 ppm of the silicon-based surfactant TSF400 (manufactured by Toshiba Silicone Co., Ltd.) was changed to 200 ppm of DC3PA (manufactured by Toray Dow Corning Silicone Co., Ltd.), and the surfactant having a fluorine atom was not added. Thus, varnish W16 of the photosensitive polyimide precursor composition was obtained. The results of evaluation in the same manner as in Example 1 using the obtained varnish W16 are shown in Table 2.

Comparative Example 9
10 g of the polyamic acid obtained in Example 1 and 2.0 g of the quinonediazide compound obtained in Synthesis Example 2 were dissolved in a mixed solvent of 20 g of γ-butyrolactone and 20 g of ethyl lactate to prepare a photosensitive polyimide precursor composition. 1130 ppm of surfactant 1H, 1H-tridecafluoroheptyl isocyanate (manufactured by Daikin Chemicals Sales Co., Ltd.) containing fluorine atoms was added thereto to obtain a photosensitive polyimide precursor composition varnish W17. The results of evaluation in the same manner as in Example 1 using the obtained varnish W17 are shown in Table 2.

Comparative Example 10
100 g of the alkali-soluble resin A1 obtained in Synthesis Example 3, 22 g of the quinonediazide compound represented by the following chemical formula (7), and (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate as a cationic polymerization initiator A photosensitive resin composition was prepared by dissolving in 2 g, 291 g of ethyl 3-ethoxypropionate, 291 g of diethylene glycol methyl ethyl ether, 32 g of butyl acetate, and 32 g of butyl lactate.

  There, 100 ppm of the silicon-based surfactant obtained in Synthesis Example 4 and 100 ppm of SH8400 (manufactured by Toray Dow Corning Silicone Co., Ltd.), a surfactant 3-perfluorooctyl-1,2-epoxy having a fluorine atom 200 ppm of propane was added at 23 ° C. to obtain a varnish W18 of a photosensitive resin composition. The results of evaluation in the same manner as in Example 1 using the obtained varnish W18 are shown in Table 2.

Comparative Example 11
100 g of the polyamide A2 obtained in Synthesis Example 5 and 25 g of the quinonediazide compound obtained in Synthesis Example 2 and 62 ppm of a fluorosurfactant FC-170C (manufactured by Sumitomo 3M Limited) were dissolved in 200 g of NMP and stirred for 3 hours. . Thereafter, stirring was stopped and the mixture was allowed to stand at room temperature to obtain a photosensitive resin composition varnish W19. The results of evaluation in the same manner as in Example 1 using the obtained varnish W19 are shown in Table 2.

Comparative Example 12
m-cresol: p-cresol = 5: 5 (weight ratio) 10 g of novolak resin obtained by condensation polymerization of cresol and formaldehyde in the presence of oxalic acid, and 2,3,4,4′-tetrahydroxybenzophenone Quinonediazide compound 2.9 g obtained from 1,2-naphthoquinonediazide-5-sulfonic acid chloride is dissolved in a mixed solvent of propylene glycol monomethyl ether acetate 61.2 g and ethyl lactate 6.8 g to obtain a photosensitive resin composition. Produced. Thereto, 600 ppm of a silicon surfactant SH29PA (manufactured by Toray Dow Corning Silicone Co., Ltd.) was added to obtain a photosensitive resin composition varnish W20. The results of evaluation in the same manner as in Example 1 using the obtained varnish W20 are shown in Table 2.

Comparative Example 13
A photosensitive resin composition prepared by dissolving 10 g of the novolak resin obtained in Comparative Example 12 and 2.9 g of the quinonediazide compound obtained in Comparative Example 12 in a mixed solvent of 132.1 g of propylene glycol monomethyl ether acetate and 6.9 g of ethyl lactate. Was made. 400 ppm of surfactant Fluorard FC430 (Sumitomo 3M Co., Ltd.) having a fluorine atom was added thereto to obtain a varnish W21 of a photosensitive resin composition. The results of evaluation in the same manner as in Example 1 using the obtained varnish W21 are shown in Table 2.

Claims (3)

(A) a photosensitive resin composition containing a polyimide resin or a precursor thereof, (b) a quinonediazide compound, (c) a solvent and (d) a surfactant, wherein (d) the surfactant is (d1) When a silicon-based surfactant and (d2) a fluorine atom-containing surfactant are included, the content of (d1) in the photosensitive resin composition is X mass%, and the content of (d2) is Y mass% X> Y (Y ≠ 0), and (d) a photosensitive resin composition in which the total amount of the surfactant is 0.005% by mass or more and 0.10% by mass or less in the photosensitive resin composition. The photosensitive resin composition according to claim 1, wherein the total solid content concentration is 5% by mass or more and 20% by mass or less. The process of apply | coating the photosensitive resin composition of Claim 1 or 2 on a board | substrate using a slit coater, forming the photosensitive resin film, the process of drying this photosensitive resin film under reduced pressure, the photosensitive property dried under reduced pressure A method for producing a heat resistant resin film, comprising a step of exposing a resin film, a step of developing the exposed photosensitive resin film, and a step of heat treatment.