JP5125747B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition. More specifically, the present invention relates to a negative photosensitive resin composition that is easily dissolved in an alkaline aqueous solution before exposure and becomes insoluble in the alkaline aqueous solution upon exposure.

  Circuit pattern formation on a semiconductor integrated circuit or printed circuit board is a complicated and diverse process such as forming a resist material on the surface of a base material, exposing a predetermined location, removing unnecessary portions by etching, and cleaning the substrate surface. It is done through. For this reason, heat-resistant photosensitive materials that can be used by leaving a necessary portion of resist as an insulating material even after pattern formation by exposure and development have been used. As these materials, for example, heat-resistant photosensitive materials such as photosensitive polyimide and photosensitive polybenzoxazole have been developed and put into practical use. In these heat-resistant photosensitive materials, in recent years, a photosensitive resin composition that can be developed with an aqueous alkaline solution from a conventional development with an organic solvent has been developed in consideration of the environment.

  Further, in order to reduce the mounting area of the LSI (Large Scale Integration) package, a pin is provided outside the package such as a conventional QFP (Quad Flat Package), and this is joined to the substrate. A method of forming bumps on a package and directly bonding the package to a substrate has been used. For this reason, it is necessary to form solder bumps or the like when forming a package, and heat resistance and chemical resistance are required for an insulating material such as polyimide used for protecting an LSI chip. In particular, since the solder bump formation is performed at a high temperature using an organic acid called a flux treatment, chemical resistance higher than the conventional one is required.

  In negative photosensitive polyimide that can be developed with alkaline aqueous solution, in order to improve chemical resistance, in addition to alkali-soluble polyimides or their precursors, polymerizable compounds, and polymerization initiators, they are replaced with organic groups as thermal crosslinking agents. A photosensitive resin composition containing a compound having a methylol group (for example, see Patent Document 1) and a photosensitive resin composition containing a blocked isocyanate compound as a thermal crosslinking agent (for example, see Patent Document 2) have been proposed. . Although the chemical resistance is improved by the resin composition containing such a thermal crosslinking agent, in the case of a composition containing a compound having a methylol group substituted with an organic group as the thermal crosslinking agent, the curing temperature is a low temperature of 280 ° C. or lower. Conditions are still insufficient, and further improvement in chemical resistance is desired. Furthermore, in these methods, there is a problem that the film loss during development increases as the standing time from exposure to post-exposure baking increases.

In response to the problem of large film loss during development, an alkali developing negative photosensitive resin in which a photoreactive group is introduced with respect to an acidic group of an alkali-soluble polyimide or its precursor has been proposed (for example, Patent Documents). 3-5). However, these methods have a problem in that the adhesion between the film and the substrate during development with an aqueous alkali solution is poor, and the pattern is easily peeled off from the substrate.
International Publication No. 04/109403 Pamphlet JP-A-11-223946 (page 1-2) Japanese Patent Laid-Open No. 10-95848 (page 1-9) JP-A-3-220558 (page 1-3) JP 2000-147671 A (page 1-7)

  The present invention has high sensitivity, small reduction in film thickness during development, regardless of the standing time from exposure to post-exposure baking, excellent adhesion to the substrate during development, and excellent chemical resistance after curing. It aims at providing the photosensitive resin composition.

  In order to solve the above problems, the photosensitive resin composition of the present invention has the following constitution. That is, it contains (a) an alkali-soluble polyimide and / or an alkali-soluble polyimide precursor, (b) a polymerizable compound having a blocked isocyanate structure and an unsaturated bond, (c) a photopolymerization initiator, and (d) a thermal crosslinking agent. The photosensitive resin composition.

  According to the present invention, the sensitivity is high, the decrease in film thickness during development is small regardless of the exposure time from exposure to post-exposure baking, the adhesion to the substrate during development is excellent, and the chemical resistance after curing is high. Can be obtained. The photosensitive resin composition of the present invention can be suitably used for a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent element, a wiring protective insulating film of a circuit board, and the like.

  The photosensitive resin composition of the present invention comprises (a) an alkali-soluble polyimide and / or an alkali-soluble polyimide precursor, (b) a polymerizable compound having a blocked isocyanate structure and an unsaturated bond, (c) a photopolymerization initiator, and (D) It contains a thermal crosslinking agent. In such a photosensitive resin composition, the block isocyanate structure forms a hydrogen bond between polymers such as the component (a) to improve sensitivity, and at the time of development regardless of the standing time from exposure to post-exposure baking. The film thickness reduction can be suppressed, and the adhesion to the substrate can be further improved. Moreover, since the blocking agent is dissociated by the heat treatment to become a reactive isocyanate group and reacts with the acidic group in the component (a), it contributes to the formation of a crosslinked structure between the polymers together with the thermal crosslinking agent (d). It is thought that a negative pattern excellent in chemical resistance can be formed.

  The (a) alkali-soluble polyimide used in the present invention has an acidic group in the structural unit of the polymer and / or at the end of the main chain. Here, the term “terminal” refers to a portion from the end of the resin until the first imide group appears. By having an acidic group in the structural unit and / or at the end of the main chain thereof, it is well dissolved in an alkaline aqueous solution before curing, so that development with an alkaline aqueous solution is possible. Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. Such alkali-soluble polyimide is not particularly limited, but preferably has a structural unit represented by the general formula (3).

In general formula (3), R ⁶ represents a 4 to 10 valent organic group, and R ⁷ represents a 2 to 8 valent organic group. R ⁸ and R ⁹ represent a phenolic hydroxyl group, a sulfonic acid group, or a thiol group, and may be the same or different. α and β represent an integer of 0-6.

  In addition, the (a) alkali-soluble polyimide precursor used in the present invention can be a polymer having an imide ring by heating or an appropriate catalyst, and preferred examples include polyamic acid and polyamic acid ester of a polyimide precursor. . Further, these polyimide precursors have an acidic group in the structural unit and / or at the end of the main chain. Here, the term “terminal” refers to a portion from the end of the resin until the first CONH group appears. Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. By having an acidic group in the structural unit and / or at the end of the main chain, it is well dissolved in an aqueous alkali solution before curing, so that development with an aqueous alkali solution is possible. Such a polyimide precursor is not particularly limited, but preferably has a structural unit represented by the general formula (4).

In General Formula (4), R ¹⁰ represents a 2 to 10 valent organic group, and R ⁷ represents a 2 to 8 valent organic group. R ⁸ and R ⁹ represent a phenolic hydroxyl group, a sulfonic acid group or a thiol group, and R ¹¹ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and may be the same or different. α and β represent an integer of 0 to 6, and γ represents an integer of 0 to 2.

  Further, when the structural unit represented by the general formula (3) or (4) has a fluorine atom, water repellency is imparted to the interface of the film and development of the interface can be suppressed when developing with an aqueous alkali solution. Therefore, it is preferable. The fluorine atom content for each of the polyimide having the structural unit represented by the general formula (3) and the polyimide precursor having the structural unit represented by the general formula (4) is 10 in order to sufficiently obtain the effect of preventing the penetration of the interface. It is preferably 20% by weight or less from the viewpoint of solubility in an alkaline aqueous solution.

In the general formula (3), R ⁶ represents an acid dianhydride residue and is a tetravalent to 10-valent organic group. Among these, an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group is preferable.

  Specific examples of the acid dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 2,3,3 ′, 4′-biphenyltetracarboxylic acid. 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-dicarboxy Phenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid Anhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorenic dianhydride, 9,9-bis {4- (3,4-dicarboxyphenoxy) phenyl} fluorenic dianhydride, 2, 3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2- Aromatic tetracarboxylic dianhydrides such as bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentane Examples include aliphatic tetracarboxylic dianhydrides such as tracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, and acid dianhydrides having the structure shown below. be able to. These are used alone or in combination of two or more.

R ¹² represents an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ , and R ¹³ and R ¹⁴ represent a hydrogen atom, a hydroxyl group or a thiol group.

  Of these, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′- Biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic 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-dicarboxyphenyl) methane dianhydride, Screw (3,4-di Ruboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorenic dianhydride, 9,9-bis {4- (3,4-dicarboxyphenoxy) ) Phenyl} fluorenic dianhydride and acid dianhydrides having the structure shown below are preferred.

R ¹² represents an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ , and R ¹³ and R ¹⁴ represent a hydrogen atom, a hydroxyl group or a thiol group.

R ^{10 in the} general formula (4) represents a structural component of an acid, and is a divalent to 10-valent organic group. Among these, an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group is preferable.

  As the acid, in addition to the tetracarboxylic dianhydrides exemplified above, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid, bis (carboxyphenyl) propane, cyclohexanedicarboxylic acid, adipic acid And dicarboxylic acids such as aliphatic dicarboxylic acids, and the like, and tricarboxylic acids such as trimellitic acid and trimesic acid. Moreover, acids having a hydroxyl group such as hydroxyphthalic acid and hydroxytrimellitic acid can also be used. These acid components may be used alone or in combination of two or more, but it is preferable to use 1 to 40 mol% of tetracarboxylic acid.

The general formula (3) and general formula (4), R ⁷ represents a residue of a diamine, a 2-8 monovalent organic group. Among these, an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group is preferable.

  Specific examples of diamines include 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 -Phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4 -(4-aminophenoxy) phenyl} -Ter, 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 or These aromatic rings are substituted with alkyl groups or halogen atoms, aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and diamines with the structure shown below. It is below. These are used alone or in combination of two or more.

R ¹² represents an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ , and R ^{13 to} R ¹⁶ represent a hydrogen atom, a hydroxyl group or a thiol group.

  Among these, 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, 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.

R ¹² represents an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ , and R ^{13 to} R ¹⁶ represent a hydrogen atom, a hydroxyl group or a thiol group.

  Particularly preferably, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylsulfone, 4,4′-diamino Diphenylsulfone, 1,4-bis (4-aminophenoxy) benzene, diamine having the structure shown below, and the like.

R ¹² represents an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ , and R ¹³ and R ¹⁴ represent a hydrogen atom, a hydroxyl group or a thiol group.

In the general formulas (3) and (4), R ⁸ and R ⁹ represent a phenolic hydroxyl group, a sulfonic acid group, or a thiol group, and α and β represent the numbers of R ⁸ and R ⁹ , respectively. In terms of stability of the resulting photosensitive resin composition solution, α and β are preferably 4 or less.

In the general formula (4), R ¹¹ represents hydrogen or an organic group having 1 to 20 carbon atoms. In view of the stability of the resulting photosensitive resin composition solution, R ¹¹ is preferably a hydrocarbon group, but hydrogen is more preferable than the solubility of an aqueous alkali solution. In the present invention, hydrogen atoms and hydrocarbon groups can be mixed. By adjusting the amount of hydrogen and organic group of R ^11, the dissolution rate with respect to the aqueous alkali solution is changed, so that a photosensitive resin composition having an appropriate dissolution rate can be obtained by this adjustment. A preferable range is that 10% to 90% of each of R ¹¹ is a hydrogen atom. Further, sufficient alkali solubility is obtained if the number of carbon atoms in R ¹¹ is 20 or less. From the above, R ¹¹ preferably contains at least one hydrocarbon group having 1 to 20 carbon atoms, and the others are hydrogen atoms. Preferable examples when R ¹¹ is a hydrocarbon group include a methyl group, an ethyl group, a propyl group, and a butyl group.

  Moreover, in General formula (4), (gamma) represents the integer of 0-2. More preferably, it is 1 or 2.

  The polyimide having the structural unit represented by the general formula (3) and the polyimide precursor having the structural unit represented by the general formula (4) preferably have an acidic group at the end of the main chain. Such a polyimide or a precursor thereof has high alkali solubility because these acidic groups are present at the ends of the main chain. Specific examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. Such introduction of an acidic group at the end of the main chain can be performed by imparting an alkali-soluble group to the end-capping agent. As the end-capping agent, monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound and the like can be used.

  Monoamines used as end capping agents are 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-aminosali Formic 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. These are used alone or in combination of two or more.

  Acid anhydrides, monocarboxylic acids, monoacid chloride compounds and monoactive ester compounds used as end-capping agents are phthalic anhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride Acid anhydrides such as 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy- Monocarboxy such as 5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid Acids and monoacid chloride compounds in which these carboxyl groups are acid chlorides and terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-di Monoacid chloride compounds in which only monocarboxyl groups of dicarboxylic acids such as carboxynaphthalene and 2,6-dicarboxynaphthalene are acid chloride, monoacid chloride compounds and N-hydroxybenzotriazole and N-hydroxy-5-norbornene-2, Active ester compounds obtained by reaction with 3-dicarboximide are preferred. These are used alone or in combination of two or more.

  The introduction ratio of the monoamine used for the terminal blocking agent is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, preferably 60 mol% or less, particularly preferably 50, based on the total amine component. It is less than mol%. The introduction ratio of the acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound used as the end-capping agent is preferably 0.1 mol% or more, particularly preferably 5 mol%, relative to the diamine component. Or more, preferably 100 mol% or less, particularly preferably 90 mol% or less. A plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

  In the polyimide having the structural unit represented by the general formula (3), the number of repeating structural units is preferably 3 or more, more preferably 5 or more, and preferably 200 or less, more preferably 100 or less. Moreover, in the polyimide precursor which has a structural unit represented by General formula (4), 10 or more are preferable and 200 or less are preferable as the repeating number of a structural unit. If it is this range, use with the thick film of the photosensitive resin composition of this invention will be attained, and sufficient solubility with respect to an alkali developing solution can be provided.

Furthermore, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized in R ⁶ , R ⁷ and R ¹⁰ as long as the heat resistance is not lowered. Specific examples of the diamine component include those obtained by copolymerizing 1 to 10 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane, and the like.

  The alkali-soluble polyimide of component (a) used in the photosensitive resin composition of the present invention may be composed only of the structural unit represented by the general formula (3), or may be a common component with other structural units. It may be a polymer or a mixture. In that case, it is preferable to contain the structural unit represented by General formula (3) 10weight% or more of the whole polyimide, and it is more preferable to contain 20weight% or more. If it is 10 weight% or more, shrinkage | contraction at the time of thermosetting can be suppressed, and it is suitable for thick film preparation. The type and amount of structural units used for copolymerization or mixing are preferably selected within a range that does not impair the heat resistance of the polyimide obtained by the final heat treatment.

  The alkali-soluble polyimide precursor of component (a) used in the photosensitive resin composition of the present invention may be composed only of the structural unit represented by the general formula (4), and other structural units. Copolymers or mixtures thereof may be used. In that case, it is preferable to contain 50 weight% or more of the structural unit represented by General formula (4), 70 weight% or more, Furthermore, it is more preferable to contain 90 weight% or more of the whole polyimide precursor. The type and amount of structural units used for copolymerization or mixing are preferably selected within a range that does not impair the heat resistance of the polyimide obtained by the final heat treatment.

  Moreover, you may use together an alkali-soluble polyimide and an alkali-soluble polyimide precursor. From the viewpoint of shrinkage during heat treatment, alkali-soluble polyimide is preferred.

  The alkali-soluble polyimide precursor of component (a) used in the present invention, for example, replaces a part of the diamine with a monoamine that is a terminal blocking agent, or replaces an acid dianhydride with a monocarboxylic acid that is a terminal blocking agent. It is synthesized using a known method in place of an acid, an acid anhydride, a monoacid chloride compound, or a monoactive ester compound. For example, a method of reacting a tetracarboxylic dianhydride and a diamine compound (partially substituted with a monoamine) at a low temperature, a tetracarboxylic dianhydride (partially an acid anhydride, a monoacid chloride compound, or a mono A method of reacting an active ester compound) with a diamine compound, a diester obtained by tetracarboxylic dianhydride and an alcohol, and then reacting in the presence of a diamine (partially substituted with a monoamine) and a condensing agent, tetra There are methods such as a method in which a diester is obtained with carboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is acid chlorideed and reacted with a diamine (partially substituted with a monoamine).

  Moreover, the alkali-soluble polyimide of the component (a) used in the present invention obtains a polyimide precursor by using, for example, a method of synthesizing the polyimide precursor, and this is obtained by using a known imidization reaction method. A method of completely imidizing, a method of stopping imidization reaction in the middle and introducing a partially imide structure, and further mixing a partially imidized polymer with the polyimide precursor to partially imide structure Can be synthesized using a method of introducing.

Moreover, the imidation ratio of the alkali-soluble polyimide of the component (a) can be easily obtained by the following method, for example. First, measuring the infrared absorption spectrum of the polymer, absorption peaks of an imide structure caused by a polyimide (1780 cm around ^-1, 1377 cm around ^-1) to confirm the presence of. Next, the polymer was heat-treated at 350 ° C. for 1 hour, the infrared absorption spectrum was measured, and the peak intensity around 1377 cm ⁻¹ was compared to calculate the content of imide groups in the polymer before heat treatment. Find the rate.

Moreover, the terminal blocker introduce | transduced into the alkali-soluble polyimide and alkali-soluble polyimide precursor of (a) component can be easily detected with the following method. For example, by dissolving a polyimide having an end capping agent dissolved in an acidic solution and decomposing it into an amine component and an acid anhydride component which are constituent units of the polyimide, this is measured by gas chromatography (GC) or NMR measurement. The end capping agent used in the present invention can be easily detected. Apart from this, the polymer component into which the end-capping agent is introduced can also be easily detected directly by pyrolysis gas chromatography (PGC), infrared spectrum and ¹³ C-NMR spectrum measurement.

  The photosensitive resin composition of the present invention contains (b) a polymerizable compound having a blocked isocyanate structure and an unsaturated bond, so that it has high sensitivity and can be used during development regardless of the standing time from exposure to post-exposure baking. A photosensitive resin composition having a small decrease in film thickness, excellent adhesion to the substrate during development, and excellent chemical resistance after curing can be obtained.

  Since the polymerizable compound of component (b) has an unsaturated bond in the molecule, a blocked isocyanate structure is introduced into the polymer side chain obtained by photopolymerization by exposure. The blocked isocyanate group has, for example, the following polar structure, so a hydrogen bond is formed between polymer chains obtained by photopolymerization, or between a polymer obtained by photopolymerization and polyimide and / or a polyimide precursor. Therefore, alkali insolubilization of the exposed part is promoted. For this reason, it is possible to improve the sensitivity and to suppress a decrease in film thickness during development regardless of the standing time from exposure to post-exposure baking.

  In addition, when a photoreactive group is introduced with respect to an acid group of a conventionally known alkali-soluble polyimide or its precursor, the acid group that is a polar group is reduced by the introduction of the photoreactive group. However, in the present invention, since there is no decrease in such acidic groups, sufficient adhesion to the substrate can be obtained during development.

  Furthermore, the blocking agent having a blocked isocyanate structure is dissociated by heat treatment (curing) to become a reactive isocyanate group, and reacts with the acidic group of the alkali-soluble polyimide and alkali-soluble polyimide precursor of component (a). Thereby, a crosslinked structure is formed between the polymer obtained by photopolymerization and the polyimide and / or the polyimide precursor. This cross-linked structure formation is considered to improve the chemical resistance together with the later-described (d) thermal cross-linking agent.

  (B) The polymerizable compound having a blocked isocyanate structure and an unsaturated bond can be obtained by reacting a compound having an isocyanate group and an unsaturated bond in the molecule with an active hydrogen group-containing compound (blocking agent). The unsaturated bond refers to a group that can be chain-polymerized in the presence of an active species such as a radical or a cation. A saturated triple bond is mentioned, and among these, a conjugated vinyl group, an acryloyl group, and a methacryloyl group are preferable in terms of polymerizability. Although there is no restriction | limiting in particular as a compound which has an isocyanate group and an unsaturated bond in a molecule | numerator, For example, it is preferable that it is a structure represented by General formula (5) or General formula (6). By reacting such a polymerizable compound having a blocked isocyanate structure and an unsaturated bond with an active hydrogen group-containing compound (blocking agent), the compound represented by the general formula (1) or the general formula (2) is obtained. can get.

In the general formulas (5) to (6), R ¹ and R ⁴ each independently represent a hydrogen atom or a methyl group. R ² represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom of the hydrocarbon group is substituted with a group having one or more atoms selected from the group consisting of N, O, F, S and P Also good. R ² is preferably a methylene group, an ethylene group, a propylene group, a phenylene group or a group in which a part of hydrogen atoms of these groups is substituted with a methyl group or an ethyl group. a represents an integer of 1 to 3, and is particularly preferably 1 from the viewpoint of reactivity with the active hydrogen group-containing compound (blocking agent).

  Specific examples of the compound represented by the general formula (5) include 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 3-isocyanatopropyl acrylate, 3-isocyanatopropyl methacrylate, 2-isocyanato-1- Methyl ethyl acrylate, 2-isocyanato-1-methyl ethyl methacrylate, 3-acryloyloxyphenyl isocyanate, 3-methacryloyloxyphenyl isocyanate, 3-isocyanato-2-methylbutyl acrylate, 3-isocyanato-2-methylbutyl methacrylate, 4- Acryloyloxyphenyl isocyanate, 4-methacryloyloxyphenyl isocyanate, 3-acryloyloxyphenyl isocyanate, 3-methacryloyloxyphenyl isocyanate Nate, 2-acryloyloxyphenyl isocyanate, 2-methacryloyloxyphenyl isocyanate, 3,5-bis (methacryloyloxyethyl) phenyl isocyanate, 2,4-bis (acryloyloxy) phenyl isocyanate, 1,1-bis (acryloyloxymethyl) ) Ethyl isocyanate, 1,1-bis (methacryloyloxymethyl) ethyl isocyanate, and the like. Specific examples of the compound represented by the general formula (6) include acryloyl isocyanate and methacryloyl isocyanate.

  The blocking agent is not particularly limited as long as it is a compound having active hydrogen, for example, thiols, phenols, oximes, amines, imines, carbazoles, amides, imides, ureas, Examples include acetoacetic acid alkyl esters, malonic acid alkyl esters, pyrazoles, imidazoles, and triazoles. Since these dissociation temperatures are as low as about 200 ° C. or lower, these blocking agents are preferable because dissociation effectively proceeds by low-temperature heat treatment (curing) and chemical resistance is further improved.

  Specific examples of the blocking agent include thiols, methanethiol, ethanethiol, benzenethiol, phenols, phenol, o-nitrophenol, m-nitrophenol, p-nitrophenol, cresol, 1-naphthol, 2- Naphthol, oximes as acetone oxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, amines as dibutylamine, diphenylamine, aniline, imines as ethyleneimine, propyleneimine, carbazoles as unsubstituted carbazole, 1, 3,6,8-tetranitrocarbazole, 3,6-dibromocarbazole, amides such as acetanilide, acetic acid amide, ε-caprolactam, γ-butyrolactam, imide As succinimide, N-hydroxysuccinimide, maleic imide, urea as urea, ethylene urea, thiourea, acetoacetic acid alkyl ester as acetoacetic acid ethyl ester, malonic acid alkyl ester as malonic acid Diethyl ester, pyrazoles as unsubstituted pyrazole, 3,5-dimethylpyrazole, 3-acetylaminopyrazole, pyrazole-3,5-dicarboxylic acid diethyl ester, imidazoles as unsubstituted imidazole, 2-methylimidazole, 2- As ethylimidazole, 2-phenylimidazole, and triazoles, 1,2,3-triazole, 1,2,4-triazole, benzotriazole and the like are preferable.

  By reacting a compound having an isocyanate group and a polymerizable unsaturated functional group in the molecule represented by general formula (5) or general formula (6) with an active hydrogen group-containing compound (blocking agent), A compound represented by the general formula (1) or (2) as shown can be obtained.

In the general formulas (1) to (2), R ¹ and R ⁴ each independently represent a hydrogen atom or a methyl group. R ² represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom of the hydrocarbon group is substituted with a group having one or more atoms selected from the group consisting of N, O, F, S and P Also good. R ³ and R ⁵ represent active hydrogen compound residues excluding alcohols. a represents an integer of 1 to 3. A is preferably 1 in that the steric hindrance is small and the reactivity of the isocyanate group during heat treatment (curing) is higher.

  (B) The polymerizable compound having a blocked isocyanate structure and an unsaturated bond is used alone or in combination of two or more. It is preferable to contain the compound represented by the general formula (1) and / or the compound represented by the general formula (2).

  (B) The content of the polymerizable compound having a blocked isocyanate structure and an unsaturated bond and an unsaturated bond is preferably 3 parts by weight or more based on 100 parts by weight of the total amount of (a) the alkali-soluble polyimide and the alkali-soluble polyimide precursor. More preferably, it is 5 parts by weight or more, more preferably 10 parts by weight or more, particularly preferably 15 parts by weight or more, preferably 100 parts by weight or less, more preferably 80 parts by weight or less. (B) By setting the content of the component to 3 parts by weight or more, a resin composition that prevents elution of an exposed part during development, has a smaller decrease in film thickness after development, and has excellent chemical resistance after curing. When the amount is 100 parts by weight or less, whitening of the film during film formation can be suppressed.

  Moreover, the photosensitive resin composition of this invention may contain the polymeric compound which has another unsaturated bond in addition to the polymeric compound which has (b) block isocyanate structure and an unsaturated bond. Examples of the unsaturated bond include unsaturated double bonds such as vinyl group, allyl group, acryloyl group and methacryloyl group and / or unsaturated triple bonds such as propargyl group. Among these, conjugated vinyl groups and An acryloyl group and a methacryloyl group are preferable in terms of polymerizability. Further, the number of functional groups contained is preferably 1 to 6 from the viewpoint of stability, and may not be the same group. The polymerizable compound referred to here preferably has a molecular weight of 30 to 800. When the molecular weight is in the range of 30 to 800, the compatibility with the polyimide or the polyimide precursor is good, and the stability of the photosensitive resin composition solution is good.

  Examples of such polymerizable compounds include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, Methylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, styrene, α-methylstyrene, 1,2-dihydronaphthalene, 1,3-diisopropenylbenzene, 3-methylstyrene, 4-methylstyrene, 2-vinyl naphthalene, butyl acrylate, butyl methacrylate, isobutyl acrylate, hexyl acetate Rate, isooctyl acrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, 1,3-butanediol diacrylate, 1,3- Butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9 Nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, 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, N-dimethylmethacrylamide, N, N-dimethylaminopropylacrylamide, N, N-dimethylaminopropylmethacrylamide N-methylolacrylamide, 2,2,6,6-tetramethylpiperidinyl methacrylate, 2,2,6,6-tetramethyl Lupiperidinyl acrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl acrylate, AH-600 (trade name, Kyoeisha Chemical Co., Ltd.), AT-600 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), UA-306H (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), UA-306T (trade name, Kyoeisha Chemical Co., Ltd.) Manufactured), ethylene oxide modified bisphenol A diacrylate, ethylene oxide modified bisphenol A dimethacrylate, N-vinyl pyrrolidone, N-vinyl caprolactam and the like. These may be used alone or in combination of two or more.

  Of these, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, isobornyl acrylate, isobornyl methacrylate, pentaerythritol triacrylate, penta Erythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 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 diacrylate, ethylene oxide modified bisphenol A dimethacrylate, N -Vinylpyrrolidone, N-vinylcaprolactam, etc. are mentioned.

  In the present invention, in the case of containing a polymerizable compound having another unsaturated bond in addition to (b) a polymerizable compound having a blocked isocyanate structure and an unsaturated bond, the content of the other polymerizable compound is (a ) With respect to 100 parts by weight of the total amount of alkali-soluble polyimide and alkali-soluble polyimide precursor, preferably 3 parts by weight or more, more preferably 5 parts by weight or more, preferably 200 parts by weight or less, more preferably 150 parts by weight or less. It is. By setting the content to 3 parts by weight or more, elution of the exposed part during development can be prevented, and by setting the content to 200 parts by weight or less, whitening of the film during film formation can be suppressed.

  Examples of the photopolymerization initiator (c) contained in the photosensitive resin composition of the present invention include benzophenone, Michler's ketone, 4,4, -bis (diethylamino) benzophenone, 3,3,4,4, -tetra (t -Benzylphenes such as -butylperoxycarbonyl) benzophenone and benzylidenes such as 3,5-bis (diethylaminobenzylidene) -N-methyl-4-piperidone and 3,5-bis (diethylaminobenzylidene) -N-ethyl-4-piperidone 7-diethylamino-3-thenonylcoumarin, 4,6-dimethyl-3-ethylaminocoumarin, 3,3-carbonylbis (7-diethylaminocoumarin), 7-diethylamino-3- (1-methylmethylbenzimidazolyl) Coumarin, 3- (2-benzothiazolyl) -7-diethyl Coumarins such as minocoumarin, anthraquinones such as 2-t-butylanthraquinone, 2-ethylanthraquinone, 1,2-benzanthraquinone, benzoins such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, ethylene glycol di (3 -Mercaptopropionate), 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, mercapto such as 2-mercaptobenzimidazole, N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N- Glycines such as (p-chlorophenyl) glycine and N- (4-cyanophenyl) glycine, 1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2- Lopandione-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, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime), OXE02 (trade name, Ciba Specialty) Oximes such as Chemicals Co., Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-methyl-1 [4- (methylthio) phenyl] -2- Α-aminoalkylphenones such as morpholinopropan-1-one, 2,2′-bis (o-chlorophenyl) -4 , 4 ′, 5,5′-tetraphenylbiimidazole and the like. Of these, the above oximes are preferable, and 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-) is particularly preferable. Benzoyl) oxime, bis (α-isonitrosopropiophenone oxime) isophthal, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime), OXE02. These may be used alone or in combination of two or more.

  Among these, the above-mentioned benzophenones, glycines, mercaptos, oximes, α-aminoalkylphenones, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl A combination selected from biimidazoles is preferred from the viewpoint of photoreaction.

  (C) The content of the photopolymerization initiator is usually preferably 0.1 to 40 parts by weight per one type with respect to 100 parts by weight of the total amount of (a) alkali-soluble polyimide and alkali-soluble polyimide precursor, and two or more types. When combining these, the total amount is preferably 0.2 to 60 parts by weight.

  The photosensitive resin composition of the present invention contains (d) a thermal crosslinking agent. Since (d) the thermal crosslinking agent forms a crosslinked structure between the polymers of component (a) by heat treatment, chemical resistance after curing can be improved together with the polymerizable compound of component (b). In addition, the shrinkage rate can be reduced. (D) As a thermal crosslinking agent, the compound which has a thermal crosslinkable group represented by General formula (7), and a benzoxazine compound are mentioned.

In General Formula (7), R ¹⁷ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, or an R ¹⁸ CO group. R ¹⁸ represents an alkyl group having 1 to 20 carbon atoms.

  (D) As the thermal crosslinking agent, for example, ML-26X, ML-24X, ML-236TMP, 4-methylol 3M6C, ML-MC, ML-TBC (which is a trade name as described above) having one thermal crosslinkable group. DM-BI25X-F, 46DMOC, 46DMOIPP, 46DMOEP (above, products), including two types, such as Honshu Chemical Industry Co., Ltd.) and Pa type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) Name, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML- OC, dimethylol-Bis-C, dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z, DM -PFP, DML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, DML-Bis25X-PCHP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), "Nicarak (registered trademark)" MX- 290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), Ba type benzoxazine, Bm type benzoxazine (trade name, manufactured by Shikoku Chemicals Co., Ltd.), 2,6-dimethoxymethyl-4 TriML-P, TriML-35XL, TriML-TrisCR-HAP (and the like) having three such as -t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol TM-BIP-A (trade name, Asahi Organic Materials Co., Ltd.) TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), “Nicarak (registered trademark)” MX-280, “Nikarak (registered trademark)” MX-270 (above, trade name, manufactured by Sanwa Chemical Co., Ltd.), and the like as HML-TPPHBA, HML-TPPHAP, HMOM-TPPHBA, HMOM-TPHAP (Above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), “Nikarak (registered trademark)” MW-390, “Nikarak (registered trademark)” MW-100LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.) Is mentioned.

  Among these, those having two or more thermally crosslinkable groups are preferable in that the crosslink density of the cured film is increased and chemical resistance is further improved, and those containing four or more are more preferable, and those containing six or more are included. Those are more preferred.

  Among these (d) thermal crosslinking agents, for example, a compound having a methylol group substituted with a hydrogen atom of a methylol group or an alcoholic hydroxyl group is crosslinked by a reaction mechanism that directly adds to a benzene ring as follows.

  The structure of the typical (d) thermal crosslinking agent used especially preferably for the photosensitive resin composition of this invention is shown below.

  These (d) thermal crosslinking agents are used alone or in combination of two or more. (D) The content of the thermal crosslinking agent is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, with respect to (a) 100 parts by weight of the total amount of the alkali-soluble polyimide and the alkali-soluble polyimide precursor. The amount is preferably 3 parts by weight or more, particularly preferably 5 parts by weight or more, preferably 150 parts by weight or less, particularly preferably 130 parts by weight or less. (A) By making content of (d) thermal crosslinking agent 150 parts by weight or less with respect to 100 parts by weight of component, the heat resistance of the heat resistant resin composition film obtained by heat treatment of the photosensitive resin composition film is lowered. There is nothing. On the other hand, when the content is 0.5 parts by weight or more, the heat resistance of the heat resistant resin composition film is improved by the effect of increasing the molecular weight by sufficient crosslinking.

  The photosensitive resin composition of the present invention can further contain a sensitizer. Among them, by using (e) a thioxanthone compound, (c) the photopolymerization initiator is efficiently sensitized and the sensitivity is further improved.

  Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-propylthioxanthone, 4-methylthioxanthone, 4-ethylthioxanthone, 4-propylthioxanthone, 2-methyl-4-ethylthioxanthone, 2-ethyl- 4-propylthioxanthone, 2-ethyl-4-methylthioxanthone, 2-ethyl-4-propylthioxanthone, 2-propyl-4-methylthioxanthone, 2-propyl-4-ethylthioxanthone, 2,4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2,4-dipropylthioxanthone and the like are preferable.

  (E) The content of the thioxanthone compound is preferably 0.01 parts by weight or more, particularly preferably 0.05 parts by weight or more with respect to 100 parts by weight of the total amount of (a) alkali-soluble polyimide and alkali-soluble polyimide precursor. Yes, preferably 10 parts by weight or less, particularly preferably 5 parts by weight or less.

  In addition, the compound which has a phenolic hydroxyl group can be contained in order to adjust the alkali developability of the photosensitive resin composition of the present invention.

  Examples of the compound having a phenolic hydroxyl group that can be used in the present invention include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, and BisOCR-CP. , BisP-MZ, BisP-EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (Tetrakis P-DO- BPA), TrisP-HAP, TrisP-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP BisOCHP-OC, Bis236T-OCHP, methylenetris-FR-CR, BisRS-26X, BisRS-OCHP (trade name, 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.).

  Among these, preferable compounds having a phenolic hydroxyl group include, for example, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, BIR- BIPC-F. By containing the compound having a phenolic hydroxyl group, the obtained resin composition is easily dissolved in an alkali developer before exposure, hardly becomes soluble in an alkali developer upon exposure, and film loss due to development is small. Development is easy in a short time.

  The content of such a compound having a phenolic hydroxyl group is preferably 1 to 60 parts by weight, more preferably 3 to 100 parts by weight based on the total amount of (a) alkali-soluble polyimide and alkali-soluble polyimide precursor. The range is 50 parts by weight.

  Further, if necessary, surfactants, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone, methyl isobutyl are used for the purpose of improving the paintability between the photosensitive resin composition and the substrate. You may contain ketones, such as a ketone, and ethers, such as tetrahydrofuran and a dioxane. Further, inorganic particles such as silicon dioxide and titanium dioxide, polyimide powder, and the like can also be contained.

  Moreover, in order to improve the adhesiveness with a base substrate such as a silicon wafer, a silane coupling agent such as methylmethacryloxydimethoxysilane and 3-aminopropyltrimethoxysilane, a titanium chelating agent, etc. are used. You may contain 0.5-10 weight part with respect to 100 weight part of total amounts of an alkali-soluble polyimide precursor.

  In the present invention, the components (a) to (d) and the compound having a phenolic hydroxyl group are used in a state dissolved and / or dispersed in an organic solvent. As the organic solvent, those having a boiling point of 80 ° C. to 250 ° C. under atmospheric pressure are preferably used.

  Specific examples of the organic solvent preferably used in the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ale, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether. Ethers such as 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, ethyl lactate, lactic acid Acetates such as butyl, acetylacetone, methylpropylketone, methylbuty Ketones, ketones such as methyl isobutyl ketone, cyclopentanone, 2-heptanone, butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3- Alcohols such as methoxybutanol and diacetone alcohol, aromatic hydrocarbons such as toluene and xylene, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethyl Examples include acetamide, dimethyl sulfoxide, and γ-butyrolactone. These may be used alone or in combination of two or more.

  Among these, those that dissolve the component (a) and have a boiling point of 100 ° C. to 180 ° C. under atmospheric pressure are particularly preferable. If the boiling point is within this range, the solvent does not volatilize at the time of coating the composition and the coating cannot be performed, and the heat treatment temperature of the composition does not need to be increased. Absent. Further, by using a solvent that dissolves the component (a), a uniform coating film can be formed on the base substrate.

  Specific examples of particularly preferable organic solvents having such boiling point include cyclopentanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, methyl lactate, ethyl lactate, diacetone alcohol, and 3-methyl. An example is -3-methoxybutanol.

  The organic solvent used in the photosensitive resin composition of the present invention is preferably 20 parts by weight or more, particularly preferably 30 parts per 100 parts by weight of the total amount of (a) alkali-soluble polyimide and alkali-soluble polyimide precursor. It is at least part by weight, preferably at most 800 parts by weight, particularly preferably at most 500 parts by weight.

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

  A photosensitive resin composition is applied onto a substrate. A silicon wafer, ceramics, gallium arsenide, or the like is used as the substrate, but is not limited thereto. The substrate may be pretreated with a chemical solution such as a silane coupling agent or a titanium chelating agent. For example, a solution obtained by dissolving the above-described coupling agent in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc. Is subjected to surface treatment by spin coating, dipping, spray coating, steam treatment or the like. Depending on the case, reaction of a board | substrate and the said coupling agent can also be advanced by applying the temperature to 50 to 300 degreeC after that.

  Examples of the method for applying the photosensitive resin composition include spin coating using a spinner, spray coating, and roll coating. Further, the coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity and the like, but it is usually applied so that the film thickness after drying becomes 1 to 150 μm.

  Next, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin composition film. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like in the range of 50 to 150 ° 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. .

  Next, post-exposure baking is performed. As this temperature, the range of 50-180 degreeC is preferable, and the range of 60-150 degreeC is especially more preferable. The time is not particularly limited, but is preferably 10 seconds to several hours from the viewpoint of subsequent developability.

  In order to form the pattern of the photosensitive resin composition, after exposure, an unexposed portion is removed using a developer.

  As the developer, for example, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphortriamide or the like alone or methanol , Ethanol, isopropyl alcohol, methyl carbitol, ethyl carbitol, toluene, xylene, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, 2 -Used in combination with organic solvents such as heptanone, ethyl acetate, tetramethylammonium aqueous solution, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate Potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, may be used an aqueous solution of a compound showing alkalinity, such as hexamethylenediamine. In particular, an aqueous solution of tetramethylammonium, an aqueous solution of an alkaline compound such as diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, or triethylamine is preferable. In some cases, these alkaline aqueous solutions may contain polar solvents 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 singly or in combination. Good. After development, rinse 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, the film is heated at 120 to 400 ° C. to form a heat resistant resin composition film. This heat treatment is carried out for 5 minutes to 5 hours by selecting the temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature. As an example, a method of performing heat treatment at 130 ° C., 200 ° C., and 300 ° C. for 30 minutes each, or linearly raising the temperature from room temperature to 300 ° C. over 2 hours may be mentioned. In the present invention, the heating temperature is preferably 150 ° C. or higher, and more preferably 180 ° C. or higher. By setting the heating temperature to 150 ° C. or higher, dissociation of the blocking agent of the polymerizable compound (b) having a blocked isocyanate structure and an unsaturated bond proceeds and the chemical resistance after curing is further improved.

  The heat-resistant resin film formed by the photosensitive resin composition of the present invention is used for applications such as semiconductor passivation films, semiconductor element protective films, interlayer insulating films for multilayer wiring for high-density mounting, and wiring protective insulating films for circuit boards. Can be used. Further, a display device including a first electrode formed on a substrate and a second electrode provided to face the first electrode, specifically, for example, a liquid crystal display, an organic EL display, an electrochromic display, It can be used for an insulating layer of a display device (organic electroluminescent device) using an organic electroluminescent element.

  Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. In addition, evaluation of the photosensitive resin composition in an Example was performed with the following method.

The synthesized polyimide was synthesized by the method described in imidization rate each example of polyimide, first, measuring the infrared absorption spectrum of the polymer, the absorption peak (1780 cm around ^-1 imide structure caused by a polyimide, 1377 cm ^-1 Near)). Next, after heat-treating the polyimide at 350 ° C. for 1 hour in a nitrogen atmosphere, the infrared absorption spectrum is measured, and the peak intensity around 1377 cm ⁻¹ is compared to calculate the content of imide groups in the polymer before heat treatment. Then, the imidation ratio of polyimide was determined.

Preparation of photosensitive resin composition film A 6-inch silicon wafer was coated with a photosensitive resin composition (hereinafter referred to as varnish) so that the film thickness after pre-baking was 10 μm, and then hot plate (Tokyo Electron Limited). A photosensitive resin composition film was obtained by prebaking at 100 ° C. for 3 minutes using Mark-7).

Measuring method of film thickness Using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd., the refractive index was measured at 1.63.

Exposure A reticle with a pattern cut is set in an exposure machine (full wavelength stepper Spectrum 3e manufactured by Ultratech Co., Ltd.), and the pre-baked photosensitive resin film is exposed at an exposure amount of 300 mJ / cm ² (i-line conversion). Full wavelength exposure was performed.

Post-exposure baking The exposed photosensitive resin film was heat-treated at 100 ° C. for 1 minute using a hot plate (Mark-7, manufactured by Tokyo Electron Ltd.).

Development A 2.38% aqueous solution of tetramethylammonium hydroxide was sprayed for 10 seconds at 50 rotations using a Mark-7 developing device manufactured by Tokyo Electron Co., Ltd. on the photosensitive resin film baked after exposure. Thereafter, the film was allowed to stand for 40 seconds at 0 rotation, then rinsed with water at 400 rotation, shaken and dried for 10 seconds at 3000 rotation, and a film after development was obtained.

Heat treatment (cure)
The developed film was heat-treated for 60 minutes at a temperature described in each example under a nitrogen stream (oxygen concentration 20 ppm or less) using an inert oven INH-21CD (manufactured by Koyo Thermo System Co., Ltd.). Got.

Measurement of remaining film rate and shrinkage remaining film rate The remaining film rate and shrinkage remaining film rate were calculated according to the following equations.
Residual film ratio (%) = film thickness after development / film thickness after pre-baking × 100
Shrinkage residual film ratio (%) = film thickness after heat treatment ÷ film thickness after development × 100.

Evaluation of pattern peeling after development The varnish described in each example and comparative example was exposed at an exposure amount of 500 mJ / cm ² , and the exposure time from exposure to post-exposure bake was 60 minutes. The presence or absence of peeling of a 10 μm pattern was observed.

Evaluation on the influence of exposure time between exposure and post-exposure baking For the varnishes described in each Example and Comparative Example, three samples of the photosensitive resin composition film were prepared by the above-described method, and the exposure was performed at an exposure amount of 300 mJ / cm ^2. After the exposure, the film was allowed to stand for 0 minutes, 15 minutes, and 60 minutes, and after exposure, baked and developed, and the remaining film ratio was measured. When the value of the remaining film ratio for 60 minutes was left to satisfy the condition of 85% or more, it was accepted, and when it did not, it was rejected.

As 60 minutes standing time until post exposure bake the evaluation exposure sensitivity, exposure exposure amount in the range of 50-800mJ / cm ² at 50 mJ / cm ² increments to calculate the residual film rate after development, the residual film The exposure amount when the rate becomes constant was defined as the minimum exposure amount.

Evaluation of chemical resistance The exposure amount is 500 mJ / cm ² , the standing time from exposure to post-exposure baking is 0 minutes, and other conditions are 40 using a release liquid 106 manufactured by Tokyo Ohka Kogyo Co., Ltd. An immersion treatment was performed at 10 ° C. for 10 minutes, and the film thickness before and after the treatment was measured to determine the amount of film thickness reduction.

Synthesis Example 1 Synthesis of hydroxyl group-containing acid anhydride (I) 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (manufactured by Central Glass Co., Ltd., BAHF) 18.3 g under a dry nitrogen stream (0.05 mol) and 34.2 g (0.3 mol) of allyl glycidyl ether were dissolved in 100 g of gamma butyrolactone (GBL) and cooled to −15 ° C. To this, 22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of GBL was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After completion of dropping, the reaction was carried out at 0 ° C. for 4 hours. This solution was concentrated with a rotary evaporator and charged into 1 L of toluene to obtain a hydroxyl group-containing acid anhydride (I) represented by the following formula.

Synthesis Example 2 Synthesis of hydroxyl group-containing diamine compound (II) 18.3 g (0.05 mol) of BAHF was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide, and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride in 100 mL of acetone was added dropwise thereto. After completion of dropping, the mixture was reacted at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white powder was filtered off and dried in vacuum at 50 ° C.

  30 g of the powder was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon 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 palladium compound as a catalyst was removed by filtration and concentrated by a rotary evaporator to obtain a hydroxyl group-containing diamine compound (II) represented by the following formula.

Synthesis Example 3 Synthesis of Polymerizable Compound (III) Having Block Isocyanate Structure and Unsaturated Bond In a 500 ml four-necked flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 57.6 g of phenol (in a nitrogen atmosphere) 0.612 mol), 0.12 g (0.6 mmol) of phenothiazine and 0.38 g (0.6 mmol) of dibutyltin dilaurate were charged and cooled in a 15 ° C. water bath. Subsequently, 93.1 g (0.6 mol) of 2-isocyanatoethyl methacrylate (manufactured by Showa Denko KK) was dropped from the dropping funnel over 60 minutes. After completion of dropping, the reaction was carried out at 80 ° C. for 5 hours. The reaction was terminated after confirming that the absorption of the isocyanate group disappeared in the infrared absorption spectrum. After cooling to room temperature, a polymerizable compound (III) having a blocked isocyanate structure and an unsaturated bond represented by the following formula was obtained.

Synthesis Example 4 Synthesis of Compound (IV) Having Block Isocyanate Structure 2,4-Tolylene Diisocyanate in 200 ml of toluene in a 500 ml four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. 17.4 g (0.1 mol), 17.4 g (0.2 mol) of methyl ethyl ketoxime, and 20.2 mg (0.2 mmol) of triethylamine were charged and reacted at 80 ° C. for 3 hours. The reaction was terminated after confirming that the absorption of the isocyanate group disappeared in the infrared absorption spectrum. After cooling to room temperature, a compound (IV) having a blocked isocyanate structure represented by the following formula was obtained.

  The polymerizable compound having an unsaturated bond, the blocked isocyanate structure and the polymerizable compound having an unsaturated bond used in each Example and Comparative Example are shown below.

Example 1
Under a dry nitrogen stream, 29.3 g (0.08 mol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane (manufactured by Central Glass Co., Ltd., BAHF), 1,3-bis (3-aminopropyl) 1.24 g (0.005 mol) of tetramethyldisiloxane and 3.27 g (0.03 mol) of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) as an end-capping agent were added to N-methyl-2-pyrrolidone. (NMP) Dissolved in 150 g. Bis (3,4-dicarboxyphenyl) ether dianhydride (manac Co., Ltd., ODPA) 31.0 g (0.1 mol) was added together with NMP 50 g, and the mixture was stirred at 20 ° C. for 1 hour, and then 50 Stir at 4 ° C. for 4 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 150 ° C. for 5 hours while azeotropically distilling water with xylene. After stirring, the solution was poured into 3 L of water to collect a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 ° C. for 20 hours. The resulting polymer powder was measured by infrared absorption spectrum, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide near 1377 cm ^-1 was detected. The imidation ratio of the polymer powder thus obtained was 100%.

  Next, 10 g of this polymer powder was charged with 1.0 g of photopolymerization initiator OXE-02 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), sensitizer 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd.) 0.10 g, thermal crosslinker “NIKALAC” MX-280 (trade name, manufactured by Sanwa Chemical Co., Ltd.) 2.0 g, polymerizable compound having an unsaturated bond, trimethylolpropane triacrylate 4 1.0 g, 1.0 g of a polymerizable compound having a blocked isocyanate structure and an unsaturated bond, “Karenz (registered trademark)” MOI-BP (trade name, manufactured by Showa Denko KK), dissolved in 15 g of diacetone alcohol, is photosensitized. The varnish A of the functional resin composition was obtained. Using the obtained varnish A, as described above, a photosensitive resin composition film was prepared on a silicon wafer, exposed to light, exposed to light, subjected to alkali development, and heat-treated at 200 ° C. for 60 minutes. Presence / absence, remaining film rate, shrinkage remaining film rate, sensitivity evaluation, and chemical resistance evaluation were performed.

Example 2
Photopolymerization initiator OXE-01 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.0 g, sensitizer 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd.) was added to 10 g of the polymer powder obtained in Example 1. 0.10 g), “NIKARAC” MW-100LM (trade name, manufactured by Sanwa Chemical Co., Ltd.) 2.0 g, a polymerizable compound having an unsaturated bond, pentaerythritol triacrylate 4.0 g, 1.5 g of “Karenz” MOI-BM (trade name, manufactured by Showa Denko KK), a polymerizable compound having a blocked isocyanate structure and an unsaturated bond, is dissolved in 15 g of γ-butyrolactone to prepare a photosensitive resin composition. A product varnish B was obtained. Using the obtained varnish B, as described above, a photosensitive resin composition film was prepared on a silicon wafer, exposed, exposed to light, baked with alkali, and heat-treated at 200 ° C. for 60 minutes. Presence / absence, remaining film rate, shrinkage remaining film rate, sensitivity evaluation, and chemical resistance evaluation were performed.

Example 3
A varnish C of a photosensitive resin composition was obtained in the same manner as in Example 2 except that the amount of addition of “Karenz” MOI-BM, which is a polymerizable compound having a blocked isocyanate structure and an unsaturated bond, was 1.0 g. Using the obtained varnish C, as described above, a photosensitive resin composition film was prepared on a silicon wafer, exposed, post-exposure baked, alkali developed, and heat-treated at 200 ° C. for 60 minutes. The presence / absence, remaining film rate, shrinkage remaining film rate, sensitivity, and chemical resistance were evaluated.

Example 4
A varnish D of a photosensitive resin composition was obtained in the same manner as in Example 2 except that the amount of addition of “Karenz” MOI-BM, which is a polymerizable compound having a blocked isocyanate structure and an unsaturated bond, was 0.5 g. Using the obtained varnish D, as described above, a photosensitive resin composition film was prepared on a silicon wafer, exposed to light, exposed to light, baked with alkali, and heat-treated at 200 ° C. for 60 minutes. The presence / absence, remaining film rate, shrinkage remaining film rate, sensitivity, and chemical resistance were evaluated.

Example 5
Under a dry nitrogen stream, BAHF 29.3 g (0.08 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 1.24 g (0.005 mol), and 3-aminophenol as an end-capping agent 3.27 g (0.03 mol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 150 g of N-methyl-2-pyrrolidone (NMP). ODPA 31.0g (0.1mol) was added here with NMP50g, and it stirred at 40 degreeC for 3 hours. Thereafter, a solution obtained by diluting 5.19 g (0.127 mol) of N, N-dimethylformamide dimethylacetal with 4 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 3 L of water to collect a white precipitate. This precipitate was collected by filtration, washed 3 times with water, and then dried for 20 hours in a vacuum dryer at 50 ° C. to obtain a polymer powder. The resulting polymer powder was measured by infrared absorption spectrum, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide near 1377 cm ^-1 was detected. The imidation ratio of the polymer powder thus obtained was 8%.

  Next, the varnish E of the photosensitive resin composition was obtained like Example 1 except using 10 g of this polymer powder. Using the obtained varnish E, as described above, a photosensitive resin composition film was prepared on a silicon wafer, exposed to light, post-exposure baked, alkali developed, and heat-treated at 230 ° C. for 60 minutes. The presence / absence, remaining film rate, shrinkage remaining film rate, sensitivity, and chemical resistance were evaluated.

Example 6
A photopolymerization initiator OXE-02 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) was added to 2.0 g of the polymer powder obtained in Example 1 and 8.0 g of the polymer powder obtained in Example 5. 0 g, sensitizer 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.) 0.10 g, thermal crosslinking agent “Nikalac” MX-100LM (trade name, manufactured by Sanwa Chemical Co., Ltd.) 1.0 g, 4.0 g of pentaerythritol triacrylate of a polymerizable compound having an unsaturated bond, “Karenz” MOI-BP (trade name, manufactured by Showa Denko KK) of a polymerizable compound having a blocked isocyanate structure and an unsaturated bond ) 1.2g was dissolved in 15g of diacetone alcohol, and the varnish F of the photosensitive resin composition was obtained. Using the obtained varnish F, as described above, a photosensitive resin composition film was prepared on a silicon wafer, exposed, exposed to light, baked with alkali, and heat-treated at 230 ° C. for 60 minutes to remove the pattern after development. The presence / absence, remaining film rate, shrinkage remaining film rate, sensitivity, and chemical resistance were evaluated.

Example 7
Under a dry nitrogen stream, 49.57 g (0.082 mol) of hydroxyl group-containing acid anhydride (I) obtained in Synthesis Example 1, and 3-hydroxyphthalic acid anhydride (Tokyo Chemical Industry Co., Ltd.) as a terminal blocking agent 5.7 g) (0.035 mol) was dissolved in 150 g of N-methyl-2-pyrrolidone (NMP). Bis (3,4-dicarboxyphenyl) ether dianhydride 31.02 g (0.1 mol) was added thereto 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. Then, it stirred at 180 degreeC for 5 hours. After stirring, the solution was poured into 3 L of water to collect a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 ° C. for 20 hours. The resulting polymer powder was measured by infrared absorption spectrum, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide near 1377 cm ^-1 was detected. The imidation ratio of the polymer powder thus obtained was 100%.

  Next, 10 g of this polymer powder was charged with 1.0 g of photopolymerization initiator OXE-01 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), sensitizer 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd.) 0.10 g, thermal crosslinking agent “NIKALAC” MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.) 1.0 g, PDBE-250, a polymerizable compound having an unsaturated bond (trade name) , Manufactured by Nippon Oil & Fats Co., Ltd.) 6.0 g, 0.8 g of “Karenz” MOI-BM (trade name, manufactured by Showa Denko KK), a polymerizable compound having a blocked isocyanate structure and an unsaturated bond, and 15 g of diethylene glycol diethyl ether The varnish G of the photosensitive resin composition was obtained. Using the obtained varnish G, as described above, a photosensitive resin composition film was prepared on a silicon wafer, exposed to light, baked after exposure, alkali developed, and heat treated at 200 ° C. for 60 minutes to remove the pattern after development. The presence / absence, remaining film rate, shrinkage remaining film rate, sensitivity, and chemical resistance were evaluated.

Example 8
Under a dry nitrogen stream, 40.5 g (0.067 mol) of the hydroxyl group-containing diamine compound (II) obtained in Synthesis Example 2 and 1.24 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane (0 0.005 mol) was dissolved in 130 g of NMP. To this, 29.42 g (0.1 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added together with 20 g of NMP, stirred at 20 ° C. for 1 hour, and then stirred at 50 ° C. for 2 hours. . 4-aminothiophenol (Tokyo Chemical Industry Co., Ltd.) 6.89g (0.055 mol) was added here, and it stirred at 50 degreeC for 2 hours, and then stirred at 180 degreeC for 5 hours. After stirring, the solution was poured into 3 L of water to collect a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 ° C. for 20 hours. The resulting polymer powder was measured by infrared absorption spectrum, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide near 1377 cm ^-1 was detected. The imidation ratio of the polymer powder thus obtained was 100%.

  Next, 10 g of this polymer powder was charged with 1.0 g of photopolymerization initiator OXE-02 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), sensitizer 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd.) 0.10 g, thermal crosslinking agent “NIKALAC” MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.) 1.0 g, PDBE-250, a polymerizable compound having an unsaturated bond (trade name) , Manufactured by Nippon Oil & Fats Co., Ltd.) 4.5 g, 1.0 g of “Karenz” MOI-BM (trade name, manufactured by Showa Denko KK), a polymerizable compound having a blocked isocyanate structure and an unsaturated bond, and 15 g of γ-butyrolactone The varnish H of the photosensitive resin composition was obtained. Using the obtained varnish H, as described above, a photosensitive resin composition film was prepared on a silicon wafer, exposed to light, baked after exposure, alkali developed, and heat-treated at 200 ° C. for 60 minutes. The presence / absence, remaining film rate, shrinkage remaining film rate, sensitivity, and chemical resistance were evaluated.

Example 9
Photosensitive resin composition in the same manner as in Example 1 except that the compound (III) obtained in Synthesis Example 3 was used instead of “Karenz” MOI-BP as the polymerizable compound having a blocked isocyanate structure and an unsaturated bond. The product varnish I was obtained. Using the obtained varnish I, as described above, a photosensitive resin composition film was prepared on a silicon wafer, exposed to light, baked after exposure, subjected to alkali development, and heat-treated at 200 ° C. for 60 minutes. The presence / absence, remaining film rate, shrinkage remaining film rate, sensitivity, and chemical resistance were evaluated.

Example 10
A photosensitive resin composition varnish J was obtained in the same manner as in Example 1 except that 2,4-diethylthioxanthone as a sensitizer was not added. Using the obtained varnish J, as described above, a photosensitive resin composition film was prepared on a silicon wafer, exposed to light, exposed to light, baked with alkali, and heat-treated at 200 ° C. for 60 minutes. The presence / absence, remaining film rate, shrinkage remaining film rate, sensitivity, and chemical resistance were evaluated.

Comparative Example 1
A varnish K of the photosensitive resin composition was obtained in the same manner as in Example 1 except that “Karenz” MOI-BP, which is a polymerizable compound having a blocked isocyanate structure and an unsaturated bond, was not added. Using the obtained varnish K, as described above, a photosensitive resin composition film was prepared on a silicon wafer, exposed to light, exposed to light, alkali developed, and heat treated at 200 ° C. for 60 minutes to remove the pattern after development. The presence / absence, remaining film rate, shrinkage remaining film rate, sensitivity, and chemical resistance were evaluated.

Comparative Example 2
A varnish L of a photosensitive resin composition was obtained in the same manner as in Example 2 except that the “Karenz” MOI-BM, which is a polymerizable compound having a blocked isocyanate structure and an unsaturated bond, was not added. Using the obtained varnish L, as described above, a photosensitive resin composition film was prepared on a silicon wafer, exposed to light, baked after exposure, alkali developed, and heat-treated at 200 ° C. for 60 minutes. The presence / absence, remaining film rate, shrinkage remaining film rate, sensitivity, and chemical resistance were evaluated.

Comparative Example 3
A varnish M of a photosensitive resin composition was obtained in the same manner as in Example 5 except that “Karenz” MOI-BP, which is a polymerizable compound having a blocked isocyanate structure and an unsaturated bond, was not added. Using the obtained varnish M, as described above, a photosensitive resin composition film was prepared on a silicon wafer, exposed to light, baked after exposure, alkali developed, and heat treated at 230 ° C. for 60 minutes to remove the pattern after development. The presence / absence, remaining film rate, shrinkage remaining film rate, sensitivity, and chemical resistance were evaluated.

Comparative Example 4
Photosensitive resin composition in the same manner as in Example 1 except that benzyl methacrylate, which is a polymerizable compound having an unsaturated bond, is added instead of “Karenz” MOI-BP, which is a polymerizable compound having a blocked isocyanate structure and an unsaturated bond. The product varnish N was obtained. Using the obtained varnish N, as described above, a photosensitive resin composition film was prepared on a silicon wafer, exposed, baked after exposure, alkali-developed, heat-treated at 200 ° C. for 60 minutes. The presence / absence, remaining film rate, shrinkage remaining film rate, sensitivity, and chemical resistance were evaluated.

Comparative Example 5
Similar to Example 2 except that N, N-dimethylaminoethyl methacrylate, which is a polymerizable compound having an unsaturated bond, is added instead of “Karenz” MOI-BM, which is a polymerizable compound having a blocked isocyanate structure and an unsaturated bond. Thus, a varnish O of the photosensitive resin composition was obtained. Using the obtained varnish O, as described above, a photosensitive resin composition film was prepared on a silicon wafer, exposed to light, exposed to light, subjected to alkali development, and subjected to heat treatment at 200 ° C. for 60 minutes. The presence / absence, remaining film rate, shrinkage remaining film rate, sensitivity, and chemical resistance were evaluated.

Comparative Example 6
Photosensitive resin composition in the same manner as in Example 7 except that cyclohexyl methacrylate, which is a polymerizable compound having an unsaturated bond, is added in place of “Karenz” MOI-BM, which is a polymerizable compound having a blocked isocyanate structure and an unsaturated bond. A product varnish P was obtained. Using the obtained varnish P, a photosensitive resin composition film was prepared on a silicon wafer as described above, exposed to light, post-exposure baked, alkali developed, and heat treated at 200 ° C. for 60 minutes. The presence / absence, remaining film rate, shrinkage remaining film rate, sensitivity, and chemical resistance were evaluated.

Comparative Example 7
Example 1 except that the polymerizable compound N, N-dimethylaminopropyl methacrylamide having an unsaturated bond is added instead of the “carenz” MOI-BP of a polymerizable compound having a blocked isocyanate structure and an unsaturated bond. Similarly, the varnish Q of the photosensitive resin composition was obtained. Using the obtained varnish Q, as described above, a photosensitive resin composition film was prepared on a silicon wafer, exposed to light, baked after exposure, subjected to alkali development, and heat treated at 200 ° C. for 60 minutes. The presence / absence, remaining film rate, shrinkage remaining film rate, sensitivity, and chemical resistance were evaluated.

Comparative Example 8
AT-600 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) of a polymerizable compound (urethane acrylate) having an unsaturated bond instead of the “Karenz” MOI-BP of a polymerizable compound having a blocked isocyanate structure and an unsaturated bond A varnish R of the photosensitive resin composition was obtained in the same manner as in Example 1 except that it was added. Using the obtained varnish R, as described above, a photosensitive resin composition film was prepared on a silicon wafer, exposed to light, baked after exposure, subjected to alkali development, and heat-treated at 200 ° C. for 60 minutes. The presence / absence, remaining film rate, shrinkage remaining film rate, sensitivity, and chemical resistance were evaluated.

Comparative Example 9
Under a dry nitrogen stream, BAHF 29.3 g (0.08 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 1.24 g (0.005 mol), and 3-aminophenol as an end-capping agent 3.27 g (0.03 mol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 150 g of NMP. Manac Co., Ltd. product, ODPA31.0g (0.1mol) was added with NMP50g, and it stirred at 20 degreeC for 1 hour, and then stirred at 50 degreeC for 4 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 150 ° C. for 5 hours while azeotropically distilling water with xylene.

After cooling this solution to room temperature, 0.40 g (2.0 mmol) of phenothiazine and 7.44 g (0.048 mol) of isocyanate ethyl methacrylate were added and reacted at 70 ° C. for 6 hours. After stirring, the solution was poured into 3 L of water to collect a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C. for 60 hours. The resulting polymer powder was measured by infrared absorption spectrum, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide near 1377 cm ^-1 was detected. The imidation ratio of the polymer powder thus obtained was 100%.

  Next, the varnish S of the photosensitive resin composition was obtained like the comparative example 1 except using this polymer powder 10g. Using the obtained varnish S, as described above, a photosensitive resin composition film was prepared on a silicon wafer, exposed to light, baked after exposure, alkali developed, and heat-treated at 200 ° C. for 60 minutes to remove the pattern after development. The presence / absence, remaining film rate, shrinkage remaining film rate, sensitivity, and chemical resistance were evaluated.

Comparative Example 10
A varnish T of the photosensitive resin composition was obtained in the same manner as in Comparative Example 2 except that 2.0 g of the compound (IV) obtained in Synthesis Example 4 was further added as a thermal crosslinking agent. Using the obtained varnish T, a photosensitive resin composition film was prepared on a silicon wafer as described above, exposed to light, post-exposure baked, alkali developed, and heat-treated at 200 ° C. for 60 minutes. The presence / absence, remaining film rate, shrinkage remaining film rate, sensitivity, and chemical resistance were evaluated.

Comparative Example 11
A varnish U of the photosensitive resin composition was obtained in the same manner as in Example 1 except that the thermal crosslinking agent “NIKALAC” MX-280 was not added. Using the obtained varnish U, a photosensitive resin composition film was prepared on a silicon wafer as described above, exposed to light, post-exposure baked, alkali developed, and heat-treated at 200 ° C. for 60 minutes. The presence / absence, remaining film rate, shrinkage remaining film rate, sensitivity, and chemical resistance were evaluated.

  The compositions and evaluation results of Examples 1 to 10 and Comparative Examples 1 to 11 are shown in Tables 1 to 3 below.

Claims (6)

Photosensitivity containing (a) alkali-soluble polyimide and / or alkali-soluble polyimide precursor, (b) polymerizable compound having block isocyanate structure and unsaturated bond, (c) photopolymerization initiator, and (d) thermal crosslinking agent Resin composition. The (b) polymerizable compound having a blocked isocyanate structure and an unsaturated bond contains a compound represented by the general formula (1) and / or a compound represented by the general formula (2). Item 2. A photosensitive resin composition according to Item 1.

(In the above formula, R ¹ and R ⁴ each independently represents a hydrogen atom or a methyl group. R ² represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom of the hydrocarbon group represents N, O, F And may be substituted with a group having one or more atoms selected from the group consisting of S, P. R ³ and R ⁵ each represent an active hydrogen compound residue excluding alcohols, and a is an integer of 1 to 3. Represents.) The photosensitive resin composition according to claim 2, wherein a in the general formula (1) is 1. (B) The polymerizable compound having a blocked isocyanate structure and an unsaturated bond is thiols, phenols, oximes, amines, imines, carbazoles, amides, imides, ureas, alkyl acetoacetates The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is a compound obtained by using a malonic acid alkyl ester, a pyrazole, an imidazole or a triazole as a blocking agent. The photosensitive resin composition according to claim 1, wherein (a) the alkali-soluble polyimide and / or the alkali-soluble polyimide precursor has an acidic group at the main chain terminal. Furthermore, ( e ) the thioxanthone compound is contained, The photosensitive resin composition in any one of Claims 1-5 characterized by the above-mentioned.