JP2018173469A - Photosensitive resin composition film, insulation film, and wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition film that has a wide development margin, allows high resolution patterning, and can form a film having excellent heat resistance.SOLUTION: A photosensitive resin composition film has (a) alkali soluble polyimide, (b) unsaturated bond-containing compound and (c) photopolymerization initiator. Relative to the photosensitive resin composition film, a rate of a film thickness (residual film rate), after being subjected to (1) an exposure step, (2) a development step and (3) a heat curing step, is 60-80%.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition film, an insulating film made of a cured product of the photosensitive resin composition film of the present invention, and a wiring board having the insulating film of the present invention. More specifically, the present invention relates to a photosensitive resin composition film suitable for forming a permanent resist used as an insulating material even after pattern processing, the photosensitive resin composition film of the present invention, and an insulating film and a wiring board using the same.

  Conventionally, polyimide is excellent in electrical characteristics and mechanical characteristics and has high heat resistance of 300 ° C. or higher, so it is useful as a surface protection film for semiconductor elements, an interlayer insulation film, and a wiring protection insulation film for circuit boards. It is said that there is. In addition, since a resist material is used for forming a circuit of a semiconductor integrated circuit or a multilayer printed wiring board, the process includes film formation on a base material, exposure to a predetermined location, removal of unnecessary portions by etching, substrate The surface cleaning work is complicated and diverse. Therefore, in recent years, in order to reduce the number of processes, the photosensitive resin composition has been used as a permanent resist which is used as an insulating material after pattern formation.

  Many examples of polyimide-containing photosensitive resin compositions have been reported so far. Among these, it contains a closed ring polyimide that does not cause curing shrinkage of the film due to the ring closing reaction from the polyimide precursor to the polyimide, and can form a film having a high resolution pattern and excellent heat resistance. A type of polyimide-containing photosensitive resin composition (see, for example, Patent Document 1) has been proposed.

  The negative-type polyimide-containing photosensitive resin composition is subjected to exposure with a predetermined pattern shape, and then a pattern is formed by removing unnecessary portions by development.

  However, when photocuring by exposure is insufficient or when development is excessive, a predetermined pattern is dissolved in the developing solution during development, or the cross-sectional shape of the pattern becomes a reverse tapered shape. When the reverse taper shape is used for a surface protection film of a semiconductor element, an interlayer insulation film, a wiring protection insulation film of a circuit board, etc., the metal serving as a conductor is insufficiently buried, and a conduction failure is likely to occur. On the other hand, when the exposure is excessive or when the development is insufficient, a residue is generated between patterns, and a predetermined pattern cannot be obtained. In particular, in a high-resolution pattern, this phenomenon becomes remarkable, and there is a problem that a processing margin (development margin) in the development process is not sufficiently ensured.

JP 2011-17897 A

  In view of such circumstances, an object of the present invention is to provide a photosensitive resin composition film having a wide development margin, capable of forming a high-resolution pattern, and capable of forming a film having excellent heat resistance. To do.

  The present invention is a photosensitive resin composition film containing (a) an alkali-soluble polyimide, (b) an unsaturated bond-containing compound, and (c) a photopolymerization initiator, and the film thickness of the photosensitive resin composition film (1) It is the photosensitive resin composition film whose ratio (remaining film ratio) of the film thickness after passing through an exposure process, (2) development process, and (3) thermosetting process is 60 to 80%.

  According to the present invention, a photosensitive resin composition film that has a wide development margin, enables high-resolution pattern formation, and can form a film having excellent heat resistance can be obtained. Since the insulating film obtained from the photosensitive resin composition film of the present invention is excellent in electrical characteristics, mechanical characteristics, and heat resistance, it serves as a surface protective film for semiconductor elements, an interlayer insulating film, and a wiring protective insulating film for circuit boards. Useful for applications.

The photosensitive resin composition film of the present invention is a photosensitive resin composition film containing (a) an alkali-soluble polyimide, (b) an unsaturated bond-containing compound, and (c) a photopolymerization initiator. The ratio (residual film ratio) of the film thickness after passing through (1) exposure process, (2) development process, and (3) thermosetting process with respect to the film thickness of the composition film is 60 to 80%. When the remaining film ratio is less than 60%, dissolution of the pattern occurs in the development process, and the pattern cross-sectional shape becomes an inversely tapered shape. On the other hand, if the remaining film ratio exceeds 80%, a residue is likely to be generated between the patterns, so that the development margin is lowered and it is difficult to obtain a high-resolution pattern. Here, the remaining film ratio refers to the percentage of the film thickness after the (1) exposure process, (2) development process, and (3) thermosetting process with respect to the film thickness of the photosensitive resin composition film. Can be calculated.
Residual film ratio (%) = ((1) exposure step, (2) development step, and (3) film thickness after undergoing thermosetting step / photosensitive resin composition film thickness) × 100
Examples of the means for setting the remaining film ratio within the above range include a method of setting the solvent content in the photosensitive resin composition film to 5 to 15% by weight.

  The (1) exposure step, (2) development step, and (3) thermosetting step for measuring the residual film ratio are performed under the following conditions.

(1) Exposure step The photosensitive resin composition film is exposed to light transmitted through an LU0385 filter of an ultrahigh pressure mercury lamp. The amount of exposure depends on the thickness of the photosensitive resin composition film. When the thickness of the photosensitive resin composition film is less than 25 μm, the exposure amount is 500 mJ / cm ² (in terms of h-line) or more. When the thickness is 25 μm or more and less than 50 μm, the exposure dose is 1000 mJ / cm ² (in terms of h line) or more. When the thickness of the photosensitive resin composition film is 50 μm or more and less than 100 μm, the exposure dose is 2000 mJ / cm ² (h line). (Conversion) Irradiate more.

(2) Development step The exposed photosensitive resin composition film is developed using a 2.38 wt% tetramethylammonium aqueous solution. The development time depends on the thickness of the photosensitive resin composition film. When the thickness of the photosensitive resin composition film is less than 25 μm, the development time is 200 seconds or more and less than 500 seconds, and the thickness of the photosensitive resin composition film is 25 μm. When the thickness is less than 50 μm, the development time is 300 seconds or more and less than 600 seconds, and when the thickness of the photosensitive resin composition film is 50 μm or more and less than 100 μm, the development time is 400 seconds or more and less than 800 seconds.

(3) Thermosetting step The photosensitive resin composition film after development is heated in an nitrogen atmosphere (oxygen concentration 20 ppm or less) from room temperature to 200 ° C over 1 hour using an inert oven, and further at 200 ° C. Heat for 1 hour.

  The photosensitive resin composition film of the present invention is obtained by, for example, applying a photosensitive resin composition containing (a) an alkali-soluble polyimide, (b) an unsaturated bond-containing compound, and (c) a photopolymerization initiator on a support. Then, by drying this, a photosensitive resin composition film can be formed on the support. Subsequently, the photosensitive resin composition film can be obtained by peeling from the support.

  Peeling of the photosensitive resin composition film from the support is preferably performed after the photosensitive resin composition film formed on the support, which will be described later, is thermocompression bonded to the substrate, and the support is made of a transparent material. If the exposure light beam is sufficiently transmitted, the photosensitive resin composition film may be peeled off from the support after exposure. Further, in the processing step of the photosensitive resin composition film, the support may be peeled off before the development step for the purpose of preventing foreign matter from adhering to the photosensitive resin composition film when passing through the step.

  Examples of the support include a polyethylene terephthalate (PET) film, a polyphenylene sulfide film, and a polyimide film. The bonding surface between the support and the photosensitive resin composition film may be subjected to a surface treatment with silicone, a silane coupling agent, an aluminum chelating agent, polyurea or the like in order to improve adhesion and peelability. The thickness of the support is not particularly limited, but is preferably 10 to 100 μm from the viewpoint of workability.

  Examples of the method for applying the photosensitive resin composition to the support include spin coating using a spinner, spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater. Examples thereof include a comma roll coater, a gravure coater, a screen coater, and a slit die coater. Moreover, although a coating film thickness changes with coating methods, the solid content concentration of a composition, a viscosity, etc., it is preferable that the film thickness after drying is 0.5 micrometer or more and 100 micrometers or less.

  In order to protect the photosensitive resin composition film, the photosensitive resin composition film of the present invention may have a protective film on the surface thereof. Thereby, the photosensitive resin composition film surface can be protected from contaminants such as dust and dust in the atmosphere.

  Examples of the protective film include a polyethylene film, a polypropylene (PP) film, a polyester film, and a polyvinyl alcohol film. It is preferable that the protective film has a peeling force such that the photosensitive resin composition film and the protective film do not easily peel off.

  The photosensitive resin composition in the present invention contains a closed ring (a) alkali-soluble polyimide, so that it differs from a resin composition film containing a polyimide precursor. There is no need to convert to Therefore, high heat resistance can be obtained without requiring heat treatment at a high temperature, and stress due to curing shrinkage due to the imide ring closure reaction can be reduced. In addition, by containing (a) an alkali-soluble polyimide, (b) an unsaturated bond-containing compound, and (c) a photopolymerization initiator, it is easily dissolved in an alkali developer before exposure, but after exposure, alkali development A negative pattern that becomes insoluble in the liquid can be formed.

  The (a) alkali-soluble polyimide in the photosensitive resin composition in the present invention refers to a polyimide having a solubility in a 2.38 wt% tetramethylammonium aqueous solution of 0.1 g / 100 g or more at a temperature of 23 ° C.

  (A) The alkali-soluble polyimide preferably has a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group and / or a thiol group at the end of the main chain, and can improve alkali solubility.

  In view of practicality with respect to an alkaline developer generally used in the semiconductor industry, it preferably has a phenolic hydroxyl group or a thiol group. The introduction of a carboxyl group, phenolic hydroxyl group, sulfonic acid group or thiol group at the end of the main chain can be carried out by using an end-capping agent having these groups. By sealing the end, the number of repeating units of (a) alkali-soluble polyimide is appropriately reduced, so that the workability of the fine pattern can be improved.

  The alkali-soluble polyimide having a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group and / or a thiol group at the main chain terminal has a structure represented by the following general formula (1) or the following general formula (2). preferable.

  In general formulas (1) to (2), X represents a monovalent organic group having at least one carboxyl group, phenolic hydroxyl group, sulfonic acid group and / or thiol group, Y represents a carboxyl group, phenolic hydroxyl group, It represents a divalent organic group having at least one sulfonic acid group and / or thiol group. X and Y preferably have a phenolic hydroxyl group or a thiol group.

R ¹ represents a 4 to 14 valent organic group, R ² represents a ² to 12 valent organic group, and R ³ and R ⁴ each independently represent a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, or a thiol group. Represents a group. R ³ and R ⁴ are preferably a phenolic hydroxyl group or a thiol group.

  Moreover, (alpha) and (beta) represent the range of 0-10 each independently. α + β is preferably 1 or more.

  n shows the repeating number of the structural unit of a polymer, and n is the range of 3-200. N is preferably 3 or more, more preferably 5 or more, in that thick film processability can be further improved. On the other hand, n is preferably 200 or less, more preferably 100 or less, in that the solubility in an alkali developer can be improved. In each polymer chain, n is an integer, but (a) n determined by analysis from alkali-soluble polyimide may not be an integer.

In the above general formulas (1) and (2), R ¹ represents a structure derived from tetracarboxylic dianhydride and is a tetravalent to 14-valent organic group. R ¹ is preferably an organic group having 5 to 40 carbon atoms containing an aromatic group or a cyclic aliphatic group.

  Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 2,3,3 ′, 4′-biphenyltetracarboxylic acid. Dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′- Benzophenone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1- Bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-di Ruboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic Acid dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluoric acid dianhydride, 9,9-bis {4- (3,4-dicarboxyphenoxy) phenyl} fluoric acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2, Aromatic tetracarboxylic dianhydrides such as 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, butanetetracarboxylic dianhydride, 1,2,3,4-cyclane Aliphatic and tetracarboxylic dianhydrides, such as pentane tetracarboxylic dianhydride, and the like acid dianhydride having the structure shown below. Two or more of these may be contained.

Here, R ⁵ represents an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ , and R ⁶ and R ⁷ each independently represent a hydroxyl group or a thiol group.

In the general formulas (1) and (2), R ² represents a diamine-derived structure and is a divalent to divalent organic group. R ² is preferably an organic group having 5 to 40 carbon atoms containing an aromatic group or a cyclic aliphatic group.

  Examples of the diamine include bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, and bis ( Such as 3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) biphenyl, bis (3-amino-4-hydroxyphenyl) fluorene, etc. Hydroxyl group-containing diamine, thiol group-containing diamine such as dimercaptophenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylmethane, 3, 4'-Diaminodiph Nilmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4 '-Diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, benzidine, m- Phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl Bis {4- (4-aminophenoxy) pheny } 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, 9,9-bis (4-aminophenyl) fluorene Such as aromatic diamines, compounds in which at least some of the hydrogen atoms of these aromatic rings are substituted with alkyl groups or halogen atoms, cyclohexyl diamine, and methylene bis cyclohexyl amine. Any aliphatic diamine or diamine having the structure shown below can be used. Two or more of these may be contained.

Here, R ⁵ represents an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ , and R ^{6 to} R ⁹ each independently represent a hydroxyl group or a thiol group.

  Among these, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diamino Diphenylmethane, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, m -Phenylenediamine, p-phenylenediamine, 1,4-bis (4-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene and diamine having the structure shown below are preferred.

Here, R ⁵ represents an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ , and R ^{6 to} R ⁹ each independently represent a hydroxyl group or a thiol group.

In the general formulas (1) and (2), R ³ and R ⁴ each independently represent a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, or a thiol group. By adjusting the amount of the alkali-soluble group of R ³ and R ^4, the dissolution rate of the polyimide in the alkaline aqueous solution is changed, so that a photosensitive resin composition having a desired dissolution rate can be obtained.

Further, it may be copolymerized aliphatic compound having a siloxane structure into R ² without compromising the heat resistance. By copolymerizing an aliphatic compound having a siloxane structure, adhesion to the substrate can be improved. Examples of the aliphatic compound having a siloxane structure include 1,3-bis (3-aminopropyl) tetramethyldisiloxane and 1,3-bis (p-amino-phenyl) octamethylpentasiloxane in the case of diamine. Can be mentioned. It is preferable to copolymerize 1 to 10 mol% of all of these diamines.

  In the general formula (1), X is derived from a primary monoamine which is a terminal blocking agent. Examples of the primary monoamine used as a terminal blocking agent 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- Minosalicylic acid, 6-aminosalicylic 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 and the like are preferable. Two or more of these may be used.

  Moreover, in General formula (2), Y originates in the dicarboxylic anhydride which is a terminal blocker. As the acid anhydride used as the terminal blocking agent, 4-carboxyphthalic acid anhydride, 3-hydroxyphthalic acid anhydride, cis-aconitic acid anhydride and the like are preferable. Two or more of these may be contained.

  The (a) alkali-soluble polyimide in the present invention may contain an alkali-soluble polyimide other than the one having the structure represented by the general formula (1) or (2). The alkali-soluble polyimide having the structure represented by the general formula (1) or (2) is preferably contained in an amount of 30% by weight or more, based on the total weight of the alkali-soluble polyimide (a), and 60% by weight or more. Is more preferable. By containing 30% by weight or more of the alkali-soluble polyimide represented by the general formula (1) or (2), shrinkage during thermosetting can be suppressed, which is more preferable for thick film processing. The kind and amount of the (a) alkali-soluble polyimide other than the alkali-soluble polyimide having the structure represented by the general formula (1) or (2) are the heat resistance of the polyimide obtained by the final heat treatment and the solubility in the alkali developer. It is preferable to select within a range that does not impair.

  (A) The alkali-soluble polyimide can be obtained by replacing a part of the diamine with a monoamine which is a terminal blocking agent, or by replacing the tetracarboxylic dianhydride with a dicarboxylic acid anhydride which is a terminal blocking agent. It can be synthesized using the method. For example, a method of reacting tetracarboxylic dianhydride, diamine compound and monoamine at low temperature, a method of reacting tetracarboxylic dianhydride, dicarboxylic anhydride and diamine compound at low temperature, tetracarboxylic dianhydride and After obtaining a polyimide precursor using a method such as a method of reacting in the presence of a diamine, monoamine and a condensing agent after obtaining a diester with an alcohol, the obtained polyimide precursor is optionally imidized. It can be synthesized by a method of complete imidization using a reaction method.

  In the present invention, (a) the imidization rate of the alkali-soluble polyimide is preferably 70% or more, more preferably 80% or more from the viewpoint of further improving the electrical properties, mechanical properties, heat resistance, moisture resistance and residual film rate of the polyimide. More preferably, 90% or more is particularly preferable.

  Examples of the method for setting the imidization ratio in the above range include a method in which the imidation reaction is performed at a reaction temperature of 160 ° C. or higher and a reaction time of 2 hours or longer in a dry nitrogen stream.

Here, the imidation ratio of (a) alkali-soluble polyimide in the present invention can be determined by the following method. First, (a) an infrared absorption spectrum of an alkali-soluble polyimide is measured, and a peak intensity A near 1377 cm ^−1, which is an absorption peak derived from an imide structure, is obtained. Next, after the (a) alkali-soluble polyimide was heat-treated at 350 ° C. for 1 hour, the infrared absorption spectrum was measured again to determine the peak intensity B near 1377 cm ⁻¹ . The imidation ratio of (a) alkali-soluble polyimide can be calculated from the following formula.
Imidation ratio (%) = (peak intensity A ÷ peak intensity B) × 100.

(A) The end-capping agent introduced into the alkali-soluble polyimide can be detected by the following method. For example, (a) an alkali-soluble polyimide having an end-capping agent introduced therein is dissolved in an acidic solution and decomposed into an amine component and a carboxylic acid anhydride component, which are constituent units of the polyimide, and this is subjected to gas chromatography (GC). ) Or by NMR analysis, the end-capping agent can be detected. Further, the end-capping agent is also detected by directly analyzing the alkali-soluble polyimide having the end-capping agent introduced therein using a pyrolysis gas chromatograph (PGC), an infrared spectrum, and a ¹³ C NMR spectrum. be able to.

  The photosensitive resin composition in the present invention contains (b) an unsaturated bond-containing compound. Examples of the unsaturated bond-containing group include unsaturated double bond-containing groups such as vinyl group, allyl group, acryloyl group, and methacryloyl group, and unsaturated triple bond-containing groups such as propargyl group. Two or more of these may be contained. Among these, a conjugated vinyl group, an acryloyl group, and a methacryloyl group are preferable in terms of polymerizability. In addition, the number of unsaturated bonds is preferably 1 to 6 from the viewpoint of suppressing cracks in the pattern due to excessive crosslinking points due to the polymerization reaction.

  (B) Examples of unsaturated bond-containing compounds include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and trimethylolpropane diacrylate. , Trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, styrene, α-methylstyrene, 1,2-dihydronaphthalene, 1,3-diisopropenylbenzene, 3-methylstyrene, 4-methyl Styrene, 2-vinylnaphthalene, butyl acrylate, butyl methacrylate, isobutyl acrylate, hexyl Chryrate, isooctyl acrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol di Acrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tri Cyclodecanediacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol Toramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-diacryloyloxy-2-hydroxypropane, 1,3-dimethacryloyloxy-2- Hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, 2,2,6,6-tetramethylpiperidinyl methacrylate, 2,2,6,6-tetramethylpiperidinyl acrylate, N -Methyl-2,2,6,6-tetramethylpiperidinyl methacrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl acrylate, ethylene oxide modified bisphenol A , Ethylene oxide modified bisphenol A dimethacrylate, propylene oxide modified bisphenol A diacrylate, propylene oxide modified bisphenol A methacrylate, propoxylated ethoxylated bisphenol A diacrylate, propoxylated ethoxylated bisphenol A dimethacrylate, N-vinylpyrrolidone, N- Examples include vinyl caprolactam. Two or more of these may be contained.

  Of these, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, isobornyl acrylate, isobornyl methacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, Pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, 2,2,6,6-tetramethylpiperidi Nyl methacrylate, 2,2,6,6-tetramethylpiperidinyl acrylate, N-methyl-2,2,6, -Tetramethylpiperidinyl methacrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl acrylate, ethylene oxide modified bisphenol A diacrylate, ethylene oxide modified bisphenol A dimethacrylate, propylene oxide modified bisphenol A diacrylate, propylene Preferred are oxide-modified bisphenol A methacrylate, propoxylated ethoxylated bisphenol A diacrylate, propoxylated ethoxylated bisphenol A dimethacrylate, N-vinyl pyrrolidone, N-vinyl caprolactam, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene oxide modified Bisphenol A diacrylate, ethylene oxide modified bisphenol A Methacrylate, propylene oxide-modified bisphenol A diacrylate, propylene oxide-modified bisphenol A dimethacrylate are more preferred.

  The content of the (b) unsaturated bond-containing compound in the photosensitive resin composition in the present invention is (a) alkali-soluble polyimide 100 from the viewpoint of suppressing the dissolution of the pattern in the developer and obtaining a good pattern. 40 parts by weight or more is preferable and 50 parts by weight or more is more preferable with respect to parts by weight. On the other hand, the content of the (b) unsaturated bond-containing compound is preferably 100 parts by weight or less, more preferably 90 parts by weight or less, with respect to 100 parts by weight of the alkali-soluble polyimide, from the viewpoint of suppressing residues during development. preferable.

  The photosensitive resin composition in the present invention contains (c) a photopolymerization initiator. (C) Examples of the photopolymerization initiator include benzophenones such as benzophenone, Michler's ketone, 4,4, -bis (diethylamino) benzophenone, 3,3,4,4, -tetra (t-butylperoxycarbonyl) benzophenone. Benzylidenes such as 3,5-bis (diethylaminobenzylidene) -N-methyl-4-piperidone and 3,5-bis (diethylaminobenzylidene) -N-ethyl-4-piperidone, 7-diethylamino-3-nonylcoumarin, 4,6-dimethyl-3-ethylaminocoumarin, 3,3-carbonylbis (7-diethylaminocoumarin), 7-diethylamino-3- (1-methylmethylbenzimidazolyl) coumarin, 3- (2-benzothiazolyl) -7- Coumarins such as diethylaminocoumarin, 2- -Anthraquinones such as butyl anthraquinone, 2-ethylanthraquinone, 1,2-benzanthraquinone, benzoins such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, Thioxanthones such as 2,4-diisopropylthioxanthone and 2-isopropylthioxanthone, mercaptos such as ethylene glycol di (3-mercaptopropionate), 2-mercaptobenzthiazole, 2-mercaptobenzoxazole and 2-mercaptobenzimidazole N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N- (p-chlorophenyl) glycine, N- (4-cyanophenyl) glycine 1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl -1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, bis (α-isonitrosopropiophenone oxime) isophthal Oximes such as 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Α such as -butan-1-one and 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one Aminoalkyl phenones, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, and the like. Two or more of these may be contained.

  Among these, the above benzophenones, glycines, mercaptos, oximes, α-aminoalkylphenones and 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl A combination of compounds selected from biimidazoles is preferred from the viewpoint of photoreaction. More preferred are oximes, particularly preferably 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl). They are oxime, bis (α-isonitrosopropiophenone oxime) isophthal, OXE01, OXE02 (trade names, manufactured by Ciba Specialty Chemicals), N-1919, NCI-831 (trade names, manufactured by ADEKA Corporation).

  The content of (c) the photopolymerization initiator in the photosensitive resin composition of the present invention is (a) an alkali-soluble polyimide from the viewpoint of effectively advancing the photocuring reaction of the (b) unsaturated bond-containing compound during exposure. 0.1 parts by weight or more is preferable with respect to 100 parts by weight, and 1 part by weight or more is more preferable. On the other hand, the content of the (c) photopolymerization initiator is further suppressed from the residue after development, and from the viewpoint of obtaining a good pattern and suppressing the excessive photocuring reaction, the weight of the (a) alkali-soluble polyimide is 100 weight. 40 parts by weight or less is preferable with respect to parts, and 20 parts by weight or less is more preferable. When two or more kinds of photopolymerization initiators are contained, the total amount is within this range. The most preferable amount of this content is appropriately selected depending on the type of photopolymerization initiator to be selected.

  The photosensitive resin composition in the present invention preferably contains (d) a thermally crosslinkable compound. The thermally crosslinkable compound is preferably a compound containing at least one alkoxymethyl group, methylol group and / or epoxy group, and more preferably has at least two alkoxymethyl groups, methylol groups and / or epoxy groups. By having at least two of these groups, in order to form a crosslinked structure by reaction between (a) alkali-soluble polyimide and (d) thermally crosslinkable compound or (d) reaction between thermally crosslinkable compounds, The mechanical properties and chemical resistance of the cured film after heat treatment can be improved.

  (D) Among the thermally crosslinkable compounds, examples of the compound having an alkoxymethyl group or a methylol group include 46DMOC, 46DMOEP (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.), DML-PC, DML-PEP. , DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML -BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp -BPF, TML-BPE, TML-BP , TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (above, trade names, Honshu Chemical Industry Co., Ltd.), "NIKACALAC" (registered trademark) MX-290, "NIKACALAC" MX-280, "NIKACALAC" MX-270, "NIKACALAC" MX-279, "NIKACALAC" MW-100LM, "NIKACALAC "MX-750LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.) and the like. Two or more of these may be contained.

  (D) Among the thermally crosslinkable compounds, examples of the compound having an epoxy group include bisphenol A type epoxy resin, bisphenol F type epoxy resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polymethyl (glycidyloxypropyl). ) And epoxy group-containing silicone. Specifically, “Epicron” (registered trademark) 850-S, “Epicron” HP-4032, “Epicron” HP-7200, “Epicron” HP-820, “Epicron” HP-4700, “Epicron” EXA-4710 , "Epicron" HP-4770, "Epicron" EXA-859CRP, "Epicron" EXA-1514, "Epicron" EXA-4880, "Epicron" EXA-4850-150, "Epicron" EXA-4850-1000, "Epicron" EXA-4816, “Epiclon” EXA-4822 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), “Lika Resin” (registered trademark) BEO-60E, “Lika Resin” BPO-20E, “Lika Resin” HBE-100 , "Lika Resin" DME-100 (above trade name, new Hon Rika Co., Ltd.), EP-4003S, EP-4000S (trade names, manufactured by Adeka Corporation), PG-100, CG-500, EG-200 (trade names, manufactured by Osaka Gas Chemical Co., Ltd.) ), NC-3000, NC-6000 (above trade name, manufactured by Nippon Kayaku Co., Ltd.), “EPOX” (registered trademark) -MK R508, “EPOX” -MK R540, “EPOX” -MK R710, “EPOX” -MK R1710, VG3101L, VG3101M80 (above trade name, manufactured by Printec Co., Ltd.), "Celoxide" (registered trademark) 2021P, "Celoxide" 2081, "Celoxide" 2083, "Celoxide" 2085 (above, trade name, Daicel) Chemical Industry Co., Ltd.). Two or more of these may be contained.

  From the viewpoint of improving the heat resistance of the cured film, the content of the (d) thermally crosslinkable compound in the photosensitive resin composition in the present invention is 1 part by weight or more with respect to 100 parts by weight of the alkali-soluble polyimide. Is preferably 5 parts by weight or more. On the other hand, the content of (d) the heat-crosslinkable compound is preferably 70 parts by weight or less, more preferably 50 parts by weight or less, with respect to 100 parts by weight of the alkali-soluble polyimide, from the viewpoint of improving the remaining film ratio. .

  The photosensitive resin composition in the present invention may further include (d) a crosslinking agent other than the thermally crosslinkable compound, a polymerization inhibitor, a colorant, a surfactant, a silane coupling agent, a titanium chelating agent, a crosslinking agent, if necessary. You may contain an accelerator, an additive, such as a sensitizer, a dissolution regulator, a stabilizer, an antifoamer, a filler, and an organic solvent.

  Since the photosensitive resin composition in the present invention further contains a polymerization inhibitor, the concentration of excitons is adjusted, so that excessive photoresponsiveness can be suppressed and the exposure margin can be widened.

  The photosensitive resin composition in the present invention has a function of suppressing stray light from a light emitting area when used in an insulating layer of an organic electroluminescent element by containing a colorant, and a solder resist for a circuit board. When used, it has the effect of hiding the circuit wiring on the substrate. Examples of the colorant include dyes such as thermochromic dyes and pigments such as inorganic pigments and organic pigments. The colorant is preferably (a) soluble in an organic solvent that dissolves alkali-soluble polyimide and (a) compatible with alkali-soluble polyimide.

  The photosensitive resin composition in this invention can improve adhesiveness with a board | substrate by containing surfactant, a silane coupling agent, a titanium chelating agent, etc.

  As the organic solvent, those that dissolve the photosensitive resin composition are preferable, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ale, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, Ethers such as ethylene glycol dibutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, Acetates such as ethyl lactate and butyl lactate, acetone, methyl ethyl ketone, acetyl Ketones such as acetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, 2-heptanone, butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2- Alcohols such as butanol, 3-methyl-3-methoxybutanol and diacetone alcohol, aromatic hydrocarbons such as toluene and xylene, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N- Examples include dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, and γ-butyrolactone. Two or more of these may be contained.

  The photosensitive resin composition in the present invention includes, for example, (a) an alkali-soluble polyimide, (b) an unsaturated bond-containing compound, (c) a photopolymerization initiator, and (d) a thermally crosslinkable compound and other additives as necessary. It can be obtained by mixing and dissolving the product. If necessary, these can be dissolved in an organic solvent to obtain a solution having a solid content of about 20 to 70% by weight. Solid content said here points out components other than an organic solvent.

  Moreover, you may filter the photosensitive resin composition using a filter paper or a filter. The filtration method is not particularly limited, but a method of filtration by pressure filtration using a filter having a reserved particle diameter of 0.4 μm to 10 μm is preferable.

  Next, the insulating film of the present invention will be described. The insulating film of this invention consists of the hardened | cured material of the said photosensitive resin composition film.

  As an example of the method for producing an insulating film of the present invention, a method for patterning the photosensitive resin composition film of the present invention to form an insulating film will be described.

  First, when the photosensitive resin composition film has a protective film, it is peeled off and bonded by thermocompression bonding so that the photosensitive resin composition film formed on the support and the substrate face each other. The laminated body laminated | stacked in order of the photosensitive resin composition film and the support body is obtained. Examples of the thermocompression bonding method include a hot press process, a thermal laminating process, and a thermal vacuum laminating process. The thermocompression bonding temperature is preferably 40 ° C. or higher from the viewpoint of improving adhesion to the substrate and embedding. On the other hand, the thermocompression bonding temperature is preferably 150 ° C. or lower from the viewpoint of suppressing excessive curing of the photosensitive resin composition film during thermocompression bonding.

  Examples of the substrate include a silicon wafer, ceramics, gallium arsenide, an organic circuit substrate, an inorganic circuit substrate, and a substrate in which circuit constituent materials are arranged. Examples of organic circuit boards include glass-based copper-clad laminates such as glass cloth / epoxy copper-clad laminates, composite copper-clad laminates such as glass nonwoven fabrics / epoxy copper-clad laminates, polyetherimide resin substrates, Examples include heat-resistant / thermoplastic substrates such as ether ketone resin substrates and polysulfone resin substrates, polyester copper-clad film substrates, and polyimide copper-clad film substrates. Examples of inorganic circuit boards include ceramic substrates such as alumina substrates, aluminum nitride substrates, silicon carbide substrates, and metal substrates such as aluminum base substrates and iron base substrates. Examples of circuit constituent materials include conductors containing metals such as silver, gold and copper, resistors containing inorganic oxides, low dielectrics containing glassy materials and / or resins, resins and Examples thereof include a high dielectric material containing high dielectric constant inorganic particles and the like, and an insulator containing a glass-based material.

  Next, a support body is peeled from said laminated body and the photosensitive resin composition film is exposed.

The photosensitive resin composition film formed by the above method is exposed to actinic radiation through a mask having a desired pattern. Examples of actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays. In the present invention, it is preferable to use i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp. The exposure amount is preferably 250 to 2500 mJ / cm ² (in terms of h-line). In the photosensitive resin composition film, when the support is a material transparent to these rays, the exposure may be performed without peeling the support from the photosensitive resin composition film.

  After the exposure, the unexposed portion is removed using a developer to form a pattern. 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 an alkaline compound such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine or hexamethylenediamine is preferred, and an aqueous 2.38 wt% tetramethylammonium solution is more preferred. If necessary, polar solutions such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone may be added.

  Development methods include, for example, a method of spraying the developer on the coating surface, a method of immersing the coating surface in the developer, a method of applying ultrasonic waves while immersing the coating surface in the developer, and rotating the coating. And a method of spraying a developing solution. The temperature of the developer is preferably 20 to 30 ° C. The development time is preferably 100 to 900 seconds. In order to process a fine pattern or to remove a residue between patterns, further development may be performed after the unexposed portion is removed.

  After the development, a rinsing process may be performed. As the rinse liquid, water is preferable. If necessary, alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water.

  If the allowable range of development conditions increases, for example, when the resolution of a pattern at the time of development is improved, a process of baking before development may be incorporated. The baking temperature is preferably 50 ° C. or higher, and more preferably 60 ° C. or higher. On the other hand, the baking temperature is preferably 180 ° C. or lower, and more preferably 120 ° C. or lower. The baking time is preferably 5 seconds to several hours.

  After the development, an insulating film can be obtained by applying a temperature of 120 ° C. to 400 ° C. to cure. In this heat treatment (curing), the temperature may be selected and the temperature may be raised stepwise, or the temperature may be raised continuously by selecting a certain temperature range. The heating temperature is more preferably 150 ° C. or higher, and further preferably 180 ° C. or higher. On the other hand, the heating temperature is preferably 300 ° C. or lower, and more preferably 250 ° C. or lower. The heat treatment time is preferably 5 minutes to 5 hours. As an example, a method of performing heat treatment at 130 ° C. and 200 ° C. for 30 minutes each, a method of linearly raising the temperature from room temperature to 250 ° C. over 2 hours, and the like can be mentioned.

  The ratio of the film thickness of the insulating film to the film thickness of the photosensitive resin composition film (residual film ratio) is preferably 60% or more from the viewpoint that the pattern does not dissolve and the cross-sectional shape of the pattern does not become a reverse taper shape. . On the other hand, the remaining film rate is preferably 80% or less from the viewpoint that there is no residue between patterns and a high-resolution pattern can be obtained. Here, the remaining film ratio indicates the percentage of the film thickness of the insulating film with respect to the film thickness of the photosensitive resin composition film, and can be calculated from the following formula.

Residual film ratio (%) = (film thickness of insulating film / film thickness of photosensitive resin composition film) × 100
In order to make the remaining film ratio within the above range, the solvent content in the photosensitive resin composition film is preferably 5 to 15% by weight. The solvent content of the photosensitive resin composition film is such that the photosensitive resin composition film is desolvated by raising the temperature of the photosensitive resin composition film to 300 ° C. at a rate of temperature increase of 5 ° C./min before and after heat treatment with respect to the weight before heat treatment. It can be obtained from the weight difference.

  Examples of the method of setting the solvent content in the above range include a method of adjusting the drying temperature and drying time after the photosensitive resin composition is applied on the support. The drying temperature is preferably 40 ° C to 120 ° C, and the drying time is preferably 1 minute to several tens of minutes. Further, these temperatures may be combined to raise the temperature stepwise, for example, heating may be performed for 1 minute each at 50 ° C., 60 ° C., and 70 ° C. Examples of the drying device include an oven, a hot plate, and infrared rays.

  The wiring board of the present invention has the insulating film of the present invention as a wiring protective insulating film. Further, when a multilayer wiring board is formed by stacking wiring boards, the insulating film of the present invention may be provided as an interlayer insulating film.

  The use of the photosensitive resin composition film of the present invention and the insulating film obtained from them is not particularly limited, for example, a surface protective film incorporated in a substrate or package for a system using a semiconductor such as a mounting substrate or a wafer level package, The present invention can be applied to resists such as interlayer insulating films and circuit board wiring protective insulating films, various electronic components, and devices. In addition, because of its excellent heat resistance, it is particularly suitable for permanent resists, that is, adhesives for thermocompression bonding a patterned interlayer insulating film, a substrate after pattern formation, glass, a semiconductor element, etc. and an adherend. Can be used.

  The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

  The (a) alkali-soluble polyimide used in each example and comparative example was synthesized by the following method.

(Synthesis Example 1: Synthesis of alkali-soluble polyimide A)
Under a stream of dry nitrogen, 32.78 g (0.0895 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane 24 g (0.005 mol) was dissolved in 100 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP). To this was added 31.02 g (0.10 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride together with 30 g of NMP, and the mixture was stirred at 20 ° C. for 1 hour, and then stirred at 50 ° C. for 4 hours. To this, 1.09 g (0.01 mol) of 3-aminophenol was added, stirred at 50 ° C. for 2 hours, and then stirred at 180 ° C. for 5 hours to obtain a resin solution. Next, the resin solution was poured into 3 L of water to collect a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried with a vacuum dryer at 80 ° C. for 5 hours to obtain an alkali-soluble polyimide A powder represented by the general formula (1). The imidation ratio of the obtained alkali-soluble polyimide A was 94%, and the solubility in a 2.38 wt% tetramethylammonium aqueous solution at 23 ° C. was 0.5 g / 100 g or more.

(Synthesis Example 2: Synthesis of alkali-soluble polyimide B)
Under a dry nitrogen stream, 18.0 g (0.09 mol) of 4,4′-diaminophenyl ether was dissolved in 100 g of NMP. To this was added 31.02 g (0.10 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride together with 30 g of NMP, and the mixture was stirred at 20 ° C. for 1 hour, and then stirred at 50 ° C. for 4 hours. Thereafter, the mixture was stirred at 180 ° C. for 5 hours to obtain a resin solution. Next, the resin solution was poured into 3 L of water to collect a white precipitate. The precipitate is collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80 ° C. for 5 hours to obtain an alkali-soluble polyimide having no structure represented by general formula (1) or general formula (2). A powder of B was obtained. The obtained alkali-soluble polyimide B had an imidation ratio of 95% and a solubility in a 2.38 wt% tetramethylammonium aqueous solution at 23 ° C. of 0.5 g / 100 g or more.

Each material other than (a) alkali-soluble polyimide used in Examples and Comparative Examples is as follows.
(B) Unsaturated bond-containing compound / DPE-6A (trade name, manufactured by Kyoeisha Chemical Co., Ltd., dipentaerythritol hexaacrylate)
BP-6EM (trade name, manufactured by Kyoeisha Chemical Co., Ltd., ethylene oxide modified bisphenol A dimethacrylate)
(C) Photopolymerization initiator OXE01 (trade name, manufactured by Ciba Specialty Chemicals)
(D) Thermally crosslinkable compound / HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd., 4,4 ′, 4 ″ -Ethylidynetris [2,6-bis (methoxymethyl) phenol]
(E) Other additives Silane coupling agent-IM-1000 (trade name, manufactured by JX Nippon Mining & Metals).

  Evaluation methods in Examples and Comparative Examples are as follows.

<Solvent content>
15-20 mg of the photosensitive resin composition film obtained in each example and comparative example was sampled, and the solvent was removed by heating up to 300 ° C. at a temperature rising rate of 5 ° C./min in a nitrogen atmosphere. The weight was measured. The difference in weight before and after the heat treatment relative to the weight before the heat treatment was taken as the solvent content.

<Resolution>
The protective film of the photosensitive resin composition film obtained by each Example and Comparative Example was peeled off, and using a laminating apparatus (manufactured by Takatori Co., Ltd., VTM-200M), a stage temperature of 80 ° C., a roll temperature of 80 ° C., The release surface was laminated on a 4 inch silicon wafer under the conditions of a vacuum degree of 150 Pa, a sticking speed of 5 mm / second, and a sticking pressure of 0.3 MPa, to form a 30 μm photosensitive resin composition layer on the silicon wafer.

After peeling off the support film, L / S = 5/5, 10/10, 15/15, 20/20, 25/25, 30/30, 35/35, 40/40, 45/45 are applied to the exposure apparatus. , 50/50, 55/55, 60/60, 65/65, 70/70, 80/80, 90/90, and a photomask having a pattern of 100/100 μm are set so that the exposure gap becomes 10 μm. The photosensitive resin composition layer was exposed to light transmitted through an LU0385 filter of an ultrahigh pressure mercury lamp at an exposure amount of 1000 mJ / cm ² (in terms of h-line). After the exposure, it was heated on a hot plate at 110 ° C. for 5 minutes. Next, using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide, Examples 1-5 and Comparative Examples 1-2 were 300 seconds, Reference Examples 6, 8 and Reference Comparative Examples 3, 5 were 200 seconds. Reference Examples 7 and 9 and Reference Comparative Examples 4 and 6 were subjected to paddle development for 400 seconds to remove unexposed portions. Subsequently, rinsing with water was performed for 60 seconds. Thereafter, spin drying was performed to obtain a pattern. Using an inert oven, the temperature was raised from room temperature to 200 ° C. in 1 hour under a nitrogen stream (oxygen concentration of 20 ppm or less), and curing was performed at 200 ° C. for 1 hour. When the temperature reached 50 ° C. or lower, the wafer was taken out and the pattern was observed with a microscope. The case where the open line and space of the minimum dimension is 25 μm or less is indicated by ◎, the case where it is 30 μm or more and 65 μm or less is indicated by “◯”, the case where it is 70 μm or more and 100 μm or less is indicated by Δ

<Pattern shape>
With respect to the line and space pattern obtained by the method described in the <Resolution> evaluation, the silicon wafer was cut so as to be perpendicular to the line pattern, and the pattern cross section was exposed. Using an optical microscope, a pattern cross section of L / S = 100/100 μm was observed at a magnification of 200 times, and the cross-sectional shape of the pattern was evaluated. The taper angle between the substrate surface and the side surface of the pattern is measured. When the taper angle is 90 ° or less and 80 ° or more, ○, when the taper angle is less than 80 °, Δ, when the taper angle is over 90 °, × It was evaluated.

<Residue>
The protective film of the photosensitive resin composition film obtained by each Example and Comparative Example was peeled off, and using a laminating apparatus (manufactured by Takatori Co., Ltd., VTM-200M), a stage temperature of 80 ° C., a roll temperature of 80 ° C., The release surface was laminated on a 4-inch glass wafer under the conditions of a vacuum degree of 150 Pa, a sticking speed of 5 mm / second, and a sticking pressure of 0.3 MPa, and a 30 μm photosensitive resin composition layer was formed on the glass wafer.

After peeling off the support film, a photomask having an opening pattern of 20 mm square is set in the exposure apparatus so that the exposure gap is 10 μm, and the light transmitted through the LU0385 filter of the ultrahigh pressure mercury lamp is 1000 mJ / cm ² (h line The photosensitive resin composition layer was exposed with an exposure amount of (converted). After the exposure, it was heated on a hot plate at 120 ° C. for 5 minutes. Next, paddle development was performed for 300 seconds using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide to remove unexposed portions. Subsequently, rinsing with water was performed for 60 seconds. Thereafter, spin drying was performed to obtain a pattern. The total light transmittance of a 20 mm square opening pattern was measured and was defined as “total light transmittance after development”. The total light transmittance of the glass wafer was measured and defined as “total light transmittance of the glass wafer”. From the following formula, the reduction rate of the total light transmittance was calculated as a residue rate, and the residue was evaluated.
Residual rate (%) = total light transmittance of glass wafer−total light transmittance after development The residual rate is less than 1.0%, and the case where it is 1.0% or more and less than 3.0%. The case where it is 3.0% or more and less than 10.0% is Δ, and the case where it is 10.0% or more is x.
In addition, total light transmittance was calculated | required as a ratio of the transmittance | permeability light intensity with respect to incident light intensity | strength according to JISK7361-1 (1997) using Nippon Denshoku Industries Co., Ltd. NDH-7000SP.

<Residual film ratio>
The film thickness of the photosensitive resin composition film obtained in each example and comparative example was measured and was defined as “film thickness of photosensitive resin composition film”. About the sample after curing of the line and space pattern obtained by the method described in the <Resolution> evaluation, the film thickness of the line pattern of L / S = 100/100 μm was measured, and “the film thickness of the insulating film” did. The remaining film ratio was calculated by the following formula.
Residual film ratio (%) = (film thickness of insulating film / film thickness of photosensitive resin composition film) × 100
<Example 1>
(A) Polyimide A: 40 g, (b) DPE-6A: 15 g, BP-6EM: 16 g, (c) HMOM-TPHAP: 5 g, (d) OXE01: 3 g, IM-1000: 1 g of diacetone alcohol / lactic acid It melt | dissolved in the mixed solvent which is ethyl = 50/50 (weight ratio). The addition amount of the solvent was adjusted so that an additive other than the solvent was a solid content, and the solid content concentration was 48% by weight. The obtained solution was pressure filtered using a filter having a reserved particle diameter of 2 μm to obtain a photosensitive resin composition. The obtained photosensitive resin composition was applied on a support film (PET film having a thickness of 50 μm) using a comma roll coater, dried at 80 ° C. for 10 minutes, and then a protective film having a thickness. A 50 μm PP film was laminated to obtain a photosensitive resin composition film having a thickness of 30 μm.

  Table 1 shows the results of evaluating the content of solvent, resolution, residue, pattern shape, and residual film ratio by the above-described method using the obtained photosensitive resin composition film.

<Examples 2-5, Comparative Examples 1-2>
The photosensitive resin composition film was produced by the method similar to Example 1 except having changed into (a) alkali-soluble polyimide of Table 1, and drying conditions. Table 1 shows the results of evaluating the content of solvent, resolution, residue, pattern shape, and residual film ratio by the above-described method using the obtained photosensitive resin composition film.

<Reference Examples 6-7>
Table 1 shows the results of evaluating the resolution, residue, pattern shape, and remaining film ratio by changing the development time as shown in Table 1 using the photosensitive resin composition film obtained in Example 2.

<Reference Examples 8-9>
Using the photosensitive resin composition film obtained in Example 3, the development time was changed as shown in Table 1, and the results of evaluation of resolution, residue, pattern shape, and remaining film ratio are shown in Table 1.

<Reference Comparative Examples 3 to 4>
Table 1 shows the results of evaluating the resolution, residue, pattern shape, and remaining film ratio by changing the development time as shown in Table 1 using the photosensitive resin composition film obtained in Comparative Example 1.

<Reference Comparative Examples 5-6>
Using the photosensitive resin composition film obtained in Comparative Example 2, the development time was changed as described in Table 1, and the results of evaluation of resolution, residue, pattern shape, and remaining film ratio are shown in Table 1.

  As shown in Table 1, the photosensitive resin composition films obtained in Examples 1 to 5 having a residual film ratio of 60 to 80% have good resolution, residue, and pattern shape even when the development time is changed. It became. On the other hand, the photosensitive resin composition films obtained in Comparative Examples 1 and 2 having a residual film ratio of less than 60% or more than 80% resulted in a narrow processing margin with poor resolution, residue, and pattern shape. .

  It is possible to provide a photosensitive resin composition film having a wide development margin, capable of forming a high-resolution pattern, and capable of forming a film having excellent heat resistance. Since the insulating film obtained from the photosensitive resin composition film of the present invention is excellent in electrical properties, mechanical properties and heat resistance, it is used for surface protection films for semiconductor elements, interlayer insulation films, wiring protection insulation films for circuit boards, etc. Useful for.

Claims (5)

A photosensitive resin composition film containing at least (a) an alkali-soluble polyimide, (b) an unsaturated bond-containing compound, and (c) a photopolymerization initiator, wherein the film thickness of the photosensitive resin composition film is (1 A photosensitive resin composition film in which the ratio of film thickness (remaining film ratio) after passing through the exposure step, (2) development step, and (3) thermosetting step is 60 to 80%. The photosensitive resin composition film according to claim 1, wherein the (a) alkali-soluble polyimide has a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and / or a thiol group. Furthermore, the photosensitive resin composition film of Claim 1 or 2 containing (d) a heat-crosslinkable compound. The insulating film which consists of hardened | cured material of the photosensitive resin composition film in any one of Claims 1-3. A wiring board having the insulating film according to claim 4.