Positive-type photosensitive resin composition, dry film, pattern coating film and electronic parts

Abstract

To provide a positive type photosensitive resin composition which stably gives good development contrast.SOLUTION: A positive type photosensitive resin composition contains (A) a polyamic acid having a carboxyl group protected with a protective group released by the action of a base, polyimide having a phenolic hydroxyl group protected with a protective group released by the action of a base, or a polybenzoxazole precursor having a phenolic hydroxyl group protected with a protective group released by the action of a base, and (B) a photobase generating agent obtained by potentializing a basic compound having an acid dissociation constant pKa of 10.8 or more by covalent bonding.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a positive photosensitive resin composition, a dry film, a pattern coating film, and an electronic component.

Background Art

[0002] In recent years, polyimide resins and polybenzoxazole resins have attracted attention as heat-resistant resins having excellent mechanical strength and electrical insulation properties, and are widely applied as insulating materials for electronic components such as semiconductors and printed wiring boards.

[0003] As a method for forming a polyimide pattern, a method for forming a negative polyimide pattern using a polyimide precursor having a photosensitive group has been conventionally known. Recently, however, photosensitive resin compositions capable of forming a positive pattern film have been proposed. As these positive photosensitive resin compositions, photoacid generators such as quinonediazide compounds are used, but there is a problem that the circuit is easily corroded when a photoacid generator is included. On the other hand, attempts have also been made to use a photobase generator, and a composition containing an alkali-soluble resin having a phenolic hydroxyl group, a covalent bond type photobase generator, and an esterifying agent for the hydroxyl group (Patent Document 1), and a composition containing a polyimide resin in which a phenolic hydroxyl group is protected with a 9-fluorenylmethyloxycarbonyl group and a photobase generator (Patent Document 2) have been proposed.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, conventional photo-base generators may have a low basicity of the generated base (small acid dissociation constant pKa), and sufficient resolution may not be obtained. For positive photosensitive resin compositions containing a photo-base generator, further improvement in development contrast is required. In addition, a decrease in development contrast may sometimes be observed during storage, and it is required to be excellent in stability at the same time.

Means for Solving the Problems

[0006] As a result of intensive studies in view of the above, the present inventors have found that by protecting carboxyl groups and phenolic hydroxyl groups in a polymer and combining them with a specific covalent-type photo-base generator, a good development contrast can be stably provided to a positive photosensitive resin composition, and thus completed the present invention.

[0007] In the composition of the present invention, the carboxyl groups of polyamic acid, the phenolic hydroxyl groups of polyimide, and the phenolic hydroxyl groups of polybenzoxazole precursors are protected by protecting groups that are eliminated by the action of a base. Therefore, in the unexposed part, the alkali solubility is inhibited. On the other hand, in the exposed part, the protecting groups are easily eliminated by the base generated from a specific covalent-type photo-base generator, and the alkali solubility is expressed. Such a remarkable difference in alkali solubility between the unexposed part and the exposed part achieves an improvement in development contrast. Further, the present inventors have also found that by using a specific covalent-type photo-base generator, a decrease in development contrast during storage is suppressed.

[0008] The gist of the present invention is as follows. [1] (A) A polyamic acid having a carboxyl group protected by a protecting group that is eliminated by the action of a base, a polyimide having a phenolic hydroxyl group protected by a protecting group that is eliminated by the action of a base, or a polybenzoxazole precursor having a phenolic hydroxyl group protected by a protecting group that is eliminated by the action of a base, and (B) A photo-base generator obtained by latentizing a basic compound having an acid dissociation constant pKa of 10.8 or more by a covalent bond. A positive photosensitive resin composition containing [2] (B) is a general formula (1):

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Advantages of the Invention

[0009] According to the present invention, there can be provided a positive photosensitive resin composition that stably provides good development contrast, a dry film having a resin layer obtained from this composition, a cured product of this composition or the resin layer of the dry film, a semiconductor element having this cured product, a printed wiring board, and an electronic component.

[0010] The resin composition of the present invention comprises (A) a polyamic acid having a carboxyl group protected by a protecting group that is eliminated by the action of a base, a polyimide having a phenolic hydroxyl group protected by a protecting group that is eliminated by the action of a base, or a polybenzoxazole precursor having a phenolic hydroxyl group protected by a protecting group that is eliminated by the action of a base, and (B) a photo base generator formed by covalently latentizing a basic compound having an acid dissociation constant pKa of 10.8 or more. Here, the photo base generator formed by covalently latentizing a basic compound is a base generator in which the generated base is latentized using a covalent bond and the base is generated by irradiation with active energy rays such as light or electromagnetic waves, and is a covalent bond type photo base generator.

[0011] <Polymer of (A)> (A) The polymer is a polyamic acid having a carboxyl group protected by a protecting group that is eliminated by the action of a base, a polyimide having a phenolic hydroxyl group protected by a protecting group that is eliminated by the action of a base, or a polybenzoxazole precursor having a phenolic hydroxyl group protected by a protecting group that is eliminated by the action of a base. Component (A) may be used alone or in any combination of two or more in any ratio.

[0012] Examples of the polyamic acid having a carboxyl group protected by a protecting group that is eliminated by the action of a base include the general formula (2): [Chemical formula] (wherein X 1 is a tetravalent organic group, Y 1 is a divalent organic group, R 1 and R 2 are each independently a hydrogen atom or a protecting group that is eliminated by the action of a base, provided that R 1 and R 2 are not simultaneously hydrogen atoms) and include polymers having a repeating unit represented by the formula.

[0013] X 1 is a tetravalent organic group, and the number of carbon atoms of the organic group is preferably 4 to 40, more preferably 6 to 34. The organic group preferably has an aromatic ring.

[0014] Examples of the organic group having an aromatic ring include groups containing a benzene ring such as a benzene skeleton, a biphenyl skeleton, and a bisphenol skeleton. For example, the following are included, but are not limited to these.

[0015] [Chemical formula]

[0016] Y 1is a divalent organic group, and the number of carbon atoms in the organic group is preferably 4 to 40, more preferably 6 to 34. The organic group preferably has an aromatic ring.

[0017] Examples of the organic group having an aromatic ring include groups containing a benzene ring such as a benzene skeleton, a biphenyl skeleton, and a bisphenol skeleton. For example, the following are included, but not limited thereto.

[0018] Examples of the group having an aromatic ring include, but are not limited to, the following. [Chemical formula] (Here, A is a single bond, -CH 2 -, -O-, -CO-, -S-, -SO 2 -, -NHCO-, -C(CF 3 ) 2 - or -C(CH 3 ) 2 -. )

[0019] R 1 and R 2 are each independently a hydrogen atom or a protecting group that is eliminated by the action of a base, provided that R 1 and R 2 are not simultaneously hydrogen atoms. Preferably, both R 1 and R 2 are protecting groups that are eliminated by the action of a base, and more preferably they are the same.

[0020] The protecting group that is eliminated by the action of the base in the general formula (2) is a group that protects a carboxylic acid group. Examples thereof include an alkyl cyanide group and an alkyl azulene group, and preferably an alkyl cyanide group. The alkyl group in these groups includes an alkyl group having 1 to 6 carbon atoms. Specific examples of the protecting group that is eliminated by the action of a base include, but are not limited to, the following. [Chemical formula]

[0021] The polymer of general formula (2) can be prepared, for example, by mixing an acid dianhydride and a diamine in a solution to synthesize a polyamic acid, and introducing a protecting group that is eliminated by the action of a base into the carboxyl group of the polyamic acid.

[0022] Examples of the acid dianhydride include those represented by general formula (5): [Chemical formula] (wherein X 1 has the same meaning as in general formula (2).) Compounds represented thereby are included.

[0023] Examples of the dianhydride include aliphatic tetracarboxylic dianhydrides such as 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione, ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride; pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,3',3,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3',3,4'-biphenyltetracarboxylic dianhydride, 2,2',6,6'-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis[(3,4-dicarboxy)benzoyl]benzene dianhydride, 1,4-bis[(3,4-dicarboxy)benzoyl]benzene dianhydride, 2,2-bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}propane dianhydride, 2,2-bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}propane dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}ketone dianhydride, bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}ketone dianhydride, 4,4'-bis[4-(1,2-dicarboxy)phenoxy]biphenyl dianhydride, 4,4'-bis[3-(1,2-(Dicarboxy)phenoxy]biphenyl dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}ketone dianhydride, bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}ketone dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}sulfone dianhydride, bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}sulfone dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}sulfide dianhydride, bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}sulfide dianhydride, 2,2-bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(2,3- or 3,4-dicarboxyphenyl)propane dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, pyridinetetracarboxylic dianhydride, sulfonyldiphthalic anhydride, m-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3',4,4'-tetracarboxylic dianhydride and other aromatic tetracarboxylic dianhydrides such as these can be mentioned.,

[0024] Among them, preferably, 1,3,3a,4,5,9b - hexahydro - 5(tetrahydro - 2,5 - dioxo - 3 - furanyl)naphtho[1,2 - c]furan - 1,3 - dione, pyromellitic dianhydride, 3,3',4,4' - benzophenone tetracarboxylic dianhydride, 3,3',4,4' - biphenyltetracarboxylic dianhydride, 2,2',6,6' - biphenyltetracarboxylic dianhydride, bis(3,4 - dicarboxyphenyl)ether dianhydride, 2,2 - bis(3,4 - dicarboxyphenyl)-1,1,1,3,3,3 - hexafluoropropane dianhydride can be mentioned.

[0025] When using an acid dianhydride into which fluorine is introduced as the acid dianhydride or an acid dianhydride having an alicyclic skeleton, it is possible to adjust physical properties such as solubility and coefficient of thermal expansion while maintaining good transparency.

[0026] The diamine that can be used for the preparation of the polymer of general formula (2) is of general formula (6):

Chemical formula

[0027] Y 1Examples of the diamine in which Y is a divalent aromatic group include paraphenylenediamine, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 9,10-bis(4-aminophenyl)anthracene, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfoxide, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxybiphenyl, bis[4-(4-aminophenoxy)phenyl]ether, 1,1,1,3,3,3-hexafluoro-2,2-bis(4-aminophenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3-amino-4-methylphenyl)propane, metaphenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene.

[0028] Y 1 Examples of the diamine in which Y is a divalent aliphatic group include 1,1-methylxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenenediamine, hexahydro-4,7-methanoindanylenemethylenediamine, tricyclo[6.2.1.02,7]-undecylenedimethyldiamine, 4,4'-methylenebis(cyclohexylamine), isophoronediamine.

[0029] As the diamine, the general formula (7):

Chemical formula

[0030] (wherein R 28 and R 29 are each independently a divalent hydrocarbon group, R 30 and R 31 are each independently a monovalent hydrocarbon group, r is an integer of 1 or more, preferably an integer of 1 to 10.) Compounds represented by the formula can also be used.)

[0031] R 28 and R 29 Examples include alkylene groups having 1 to 7 carbon atoms such as methylene group, ethylene group, propylene group, and arylene groups having 6 to 18 carbon atoms such as phenylene group. R 30 and R 31 Examples include alkyl groups having 1 to 7 carbon atoms such as methyl group, ethyl group, and aryl groups having 6 to 12 carbon atoms such as phenyl group.

[0032] To introduce a protecting group that is eliminated by the action of a base into the carboxyl group of the polyamic acid, it can be carried out by reacting the polyamic acid with R 1 X or R 2 X (wherein X is a halogen atom, preferably a chlorine atom.), but is not limited thereto.)

[0033] Examples of the polyimide having a phenolic hydroxyl group protected by a protecting group that is eliminated by the action of a base include the general formula (3):

Chemical formula

[0034] X 2 is a (4+p)-valent organic group. The number of carbon atoms in the organic group is preferably 4 to 40, more preferably 6 to 34. The organic group preferably has an aromatic ring.

[0035] Examples of the organic group having an aromatic ring include groups containing a benzene ring such as a benzene skeleton, a biphenyl skeleton, and a bisphenol skeleton. For example, the following groups and groups to which p (OR 3 ) are attached are included, but not limited thereto.

[0036]

Chemical formula

[0037] Y 2 is a (2+q)-valent organic group. The number of carbon atoms in the organic group is preferably 4 to 40, more preferably 6 to 34. The organic group preferably has an aromatic ring.

[0038] Examples of the organic group having an aromatic ring include groups containing a benzene ring such as a benzene skeleton, a biphenyl skeleton, and a bisphenol skeleton. For example, the following groups and groups in which q (OR 4 ) are bonded thereto are included, but are not limited thereto.

[0039] Examples of the group having an aromatic ring include, but are not limited to, the following.

[0040] [Chemical formula] (Here, A is a single bond, -CH 2 -, -O-, -CO-, -S-, -SO 2 -, -NHCO-, -C(CF 3 ) 2 - or -C(CH 3 ) 2 -. )

[0041] R 3 is a hydrogen atom or a protecting group that is eliminated by the action of a base. When a plurality of R 4 are present, they may be the same or different, and are preferably the same. R 4 is a hydrogen atom or a protecting group that is eliminated by the action of a base. When a plurality of R 4 are present, they may be the same or different, and are preferably the same. p is an integer from 0 to 4, and q is an integer from 0 to 4, but p and q are not simultaneously 0. Preferably, (p + q) is an integer from 1 to 3, more preferably (p + q) is 2, particularly preferably p is 2 and q is 0, or p is 0 and q is 2.

[0042] In general formula (3), OR 3 the carbon atom to which is bonded is a ring-constituting atom of the aromatic ring, OR 4 the carbon atom to which is bonded is a ring-constituting atom of the aromatic ring, R 3 and R4 Not all of them are hydrogen atoms, and R 3 and R 4 are preferably protecting groups that are eliminated by the action of a base.

[0043] The protecting group that is eliminated by the action of the base in the general formula (3) is a protecting group for a phenolic hydroxyl group, and examples thereof include a mono- or dialkoxynitrobenzyloxycarbonyl group and a fluorenylmethyloxycarbonyl group, and preferably a fluorenylmethyloxycarbonyl group. Specific examples of the protecting group that is eliminated by the action of a base include, but are not limited to, the following.

Chemical formula

[0044] The polymer of the general formula (3) can be prepared, for example, by mixing an acid dianhydride having q phenolic hydroxyl groups and a diamine having p phenolic hydroxyl groups to synthesize a polyamic acid, cyclizing this to form a polyimide, and then introducing a protecting group that is eliminated by the action of a base into the phenolic hydroxyl groups in the polyimide.

[0045] Examples of the acid dianhydride having p phenolic hydroxyl groups include the acid dianhydrides mentioned in relation to the above general formula (2) and compounds in which p hydroxyl groups are bonded to the aromatic rings of these acid dianhydrides.

[0046] Examples of the diamine having q phenolic hydroxyl groups include the diamines listed in relation to the above general formula (2) and compounds in which q hydroxyl groups are bonded to the aromatic rings of these diamines. For example, examples of the diamine having a phenolic hydroxyl group include 2,4-diaminophenol, 3,5-diaminophenol, 2,5-diaminophenol, 1,4-diamino-2,5-dihydroxybenzene, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis(3-amino-4-hydroxyphenyl) ether, bis(4-amino-3-hydroxyphenyl) ether, bis(4-amino-3,5-dihydroxyphenyl) ether, bis(3-amino-4-hydroxyphenyl) methane, bis(4-amino-3-hydroxyphenyl) methane, 2,2-bis(3-amino-4-hydroxyphenyl) propane, 2,2-bis(3-hydroxy-4-aminophenyl) propane, bis(4-amino-3,5-dihydroxyphenyl) methane, bis(3-amino-4-hydroxyphenyl) sulfone, bis(4-amino-3-hydroxyphenyl) sulfone, bis(4-amino-3,5-dihydroxyphenyl) sulfone, 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis(4-amino-3,5-dihydroxyphenyl) hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl) hexafluoropropane, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethoxybiphenyl, 1,4-bis(3-amino-4-hydroxyphenoxy) benzene, 1,3-bis(3-amino-4-hydroxyphenoxy) benzene, 1,4-bis(4-amino-3-hydroxyphenoxy) benzene, 1,3-bis(4-amino-3-hydroxyphenoxy) benzene, bis[4-(3-amino-4-hydroxyphenoxy) phenyl] sulfone, bis[4-(3-amino-4-hydroxyphenoxy) phenyl] propane, 2,2-Bis[4-(3-amino-4-hydroxyphenoxy)phenyl]hexafluoropropane, bis(4-amino-4-carboxy-5-hydroxyphenyl)ether, bis(4-amino-3-carboxy-5-hydroxyphenyl)methane, bis(4-amino-3-carboxy-5-hydroxyphenyl)sulfone, 2,2-bis(4-amino-3-carboxy-5-hydroxyphenyl)propane, 2,2-bis(4-amino-3-carboxy-5-hydroxyphenyl)hexafluoropropane, and diamines having the following structure, etc. are mentioned, but not limited thereto.,

[0047]

Chemical formula

[0048] To introduce a protecting group that is eliminated by the action of a base to the phenolic hydroxyl group of a polyimide, it can be carried out by reacting the polyimide with R 3 X or R 4 X (where X is a halogen atom, preferably a chlorine atom). However, it is not limited thereto.,

[0049] Examples of the polybenzoxazole precursor having a phenolic hydroxyl group protected by a protecting group that is eliminated by the action of a base include the general formula (4):

Chemical formula

[0050] X 3 is a divalent organic group, which may be an aliphatic group or an aromatic group, preferably an aromatic group, and more preferably bonded to the carbonyl in the general formula (4) on the aromatic ring. The number of carbon atoms of the aromatic group is preferably 6 to 30, more preferably 6 to 24.

[0051] Examples of the aromatic group include, but are not limited to, the following.

[0052]

Chemical formula

[0053] Y 3 is a (2 + s)-valent organic group, which may be an aliphatic group or an aromatic group, preferably an aromatic group. The number of carbon atoms of the aromatic group is preferably 6 to 30, more preferably 6 to 24. It is more preferable that two (OR 5 ) and two amino groups are located ortho to each other on the aromatic ring.

[0054] Examples of the aromatic group include, for example, the following groups (assuming that (OR 5 ) is bonded to two of the bonds) or groups to which (s - 2) (OR 5 ) are bonded, but are not limited to these.

[0055]

Chemical formula

[0056] R 5is a protecting group that is eliminated by the action of a hydrogen atom or a base, and may be the same or different, but is preferably the same. s is preferably 2. In general formula (4), OR 5 The carbon atom to which it is attached is a ring-constituting atom of the aromatic ring. R 5 Not all of them are hydrogen atoms, and it is preferable that all of them are protecting groups that are eliminated by the action of a base.

[0057] The protecting group that is eliminated by the action of the base in general formula (4) is a group that protects a phenolic hydroxyl group, and examples thereof include a mono- or dialkoxynitrobenzyloxycarbonyl group and a fluorenylmethyloxycarbonyl group, and preferably a fluorenylmethyloxycarbonyl group. Specific examples of the protecting group that is eliminated by the action of a base include, but are not limited to, the following.

Chemical formula

[0058] The polymer of general formula (4) can be prepared, for example, by reacting a dihydroxydiamine with a dicarboxylic acid dihalide such as a dicarboxylic acid dichloride to introduce a protecting group that is eliminated by the action of a base into the phenolic hydroxyl group in the reaction product.

[0059] Examples of the dihydroxyamine include, but are not limited to, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, etc. Among them, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane is preferred.

[0060] Examples of the dicarboxylic acid in the dicarboxylic acid dichloride include, but are not limited to, aromatic ring-containing dicarboxylic acids such as isophthalic acid, terephthalic acid, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis(4-carboxyphenyl)sulfone, 2,2-bis(p-carboxyphenyl)propane, 2,2-bis(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, etc., and aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, etc. Among them, 4,4'-dicarboxydiphenyl ether is preferred.

[0061] To introduce a protecting group that is eliminated by the action of a base to the phenolic hydroxyl group of the reactant, it can be carried out by reacting the polyimide with R 3 X or R 4 X (where X is a halogen atom, preferably a chlorine atom). However, it is not limited thereto.

[0062] The weight average molecular weight of the polymer in (A) can be 1,000 to 1,000,000, preferably 5,000 to 100,000, and more preferably 10,000 to 50,000. The weight average molecular weight can be measured by the method described in the examples.

[0063] <Specific covalent type photo-base generator of (B)> The positive photosensitive resin composition of the present invention contains a photo-base generator in which a basic compound having an acid dissociation constant pKa of 10.8 or more is latentized by a covalent bond. By containing a specific covalent type photo-base generator, the dissolution inhibition effect of the unexposed portion is better than that in the case of containing an ionic bond type photo-base generator, and the development contrast can be improved. Further, by using a specific covalent type photo-base generator, it is also possible to suppress the decrease in the development contrast during storage.

[0064] The base generated by the covalent type photo-base generator preferably has an acid dissociation constant pKa of 10.8 or more, more preferably 13.0 or more. The acid dissociation constant pKa is a measured value in an aqueous solution at 25°C.

[0065] Examples of the generated base include, but are not limited to, 1,1,3,3-tetramethylguanidine (TMG), dibutylamine (DBA), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 2-methyl-2-imidazoline, etc.

[0066]

Chemical formula

[0067] Preferably, they are TMG and TBD.

[0068] As the photo-base generator, general formula (1):

Chemical formula

[0069] Z is represented by the general formula (z1):

Chemical formula

[0070] R 1 and R 2 are both alkyl groups from the perspective of the basicity of the generated base, or they form a cyclic structure together with the nitrogen atom to which they are attached, and it is preferred that R 1 and R 2 form an alkylene chain in the cyclic structure. The number of carbon atoms constituting the alkyl group or alkylene chain is preferably 1 to 20, more preferably 1 to 8.

[0071] Z is represented by the general formula (z2):

Chemical formula

[0072] Preferably, the following photo-base generators are included, but not limited thereto. [Chemical formula]

[0073] [Blending amount] In the positive resin composition of the present invention, with respect to 100 parts by mass of the polymer of (A), the covalent photo-base generator of (B) is preferably 10 to 40 parts by mass. Within this range, the development contrast can be sufficiently improved.

[0074] [Solvent] The positive photosensitive resin composition of the present invention can contain a solvent, and the solvent is not particularly limited as long as it can dissolve the polymer of (A) and the covalent photo-base agent of (B).

[0075] Examples of the solvent include N,N'-dimethylformamide, N-methylpyrrolidone (NMP), N-ethyl-2-pyrrolidone, N,N'-dimethylacetamide (DMAc), diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, tetrahydrofuran, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, γ-butyrolactone, diethylene glycol monomethyl ether, and the like. These may be used alone or in any combination of two or more in any ratio. The amount of the solvent is not particularly limited and can be adjusted according to, for example, the coating film thickness, viscosity, and the like. The solvent can be, for example, 50 to 9000 parts by mass with respect to 100 parts by mass of the polymer of (A).

[0076] <Other components> The positive photosensitive resin composition of the present invention can contain a sensitizer. By blending a sensitizer, the photosensitivity can be further improved. The sensitizer is not particularly limited, and examples thereof include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-dimethylaminobenzal)-4-methylcyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, etc. In terms of sensitivity, thioxanthones such as 4-(1-methylethyl)-9H-thioxanthen-9-one are preferred.These may be used alone or in any combination of two or more at any ratio. The sensitizer can be used in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the polymer of (A), for example.

[0077] The positive photosensitive resin composition of the present invention can contain a base propagator. For the decomposition of the photo base generator to be uniform in the thick film direction, it is preferable to use a base propagator in combination. The base propagator is not particularly limited, and for example, the base propagators disclosed in JP-A-2012-237776, JP-A-2006-282657, etc. can be used.

[0078] The positive photosensitive resin composition of the present invention can contain a coupling agent. By blending a coupling agent, the adhesiveness to the substrate is improved. The coupling agent is not particularly limited, and examples include silane coupling agents, etc., such as silane coupling agents having an alkoxy group, silane coupling agents having a mercapto group, silane coupling agents having an epoxy group, silane coupling agents having an ethylenically unsaturated group, and silane coupling agents having an arylamino group. Commercially available coupling agents include, for example, the KBM series and KBE series manufactured by Shin-Etsu Silicone Co., Ltd. The coupling agent can be used in an amount of 0.5 to 10 parts by mass based on 100 parts by mass of the polymer of (A), for example.

[0079] The positive photosensitive resin composition of the present invention can contain a melamine-based compound. By blending a melamine-based compound, the chemical resistance is improved. The melamine-based compound is not particularly limited, and examples include the MW series manufactured by Sanwa Chemical Co., Ltd. The positive photosensitive resin composition of the present invention can contain a crosslinking agent having a methylol group. By blending a crosslinking agent having a methylol group, the resolution and mechanical properties are improved. Examples include TM-BIP-A manufactured by Asahi Organic Materials Co., Ltd. and TML-BPAF-MF manufactured by Honshu Chemical Co., Ltd.

[0080] The positive photosensitive resin composition of the present invention can contain a filler. The filler is not particularly limited and may be either an inorganic filler or an organic filler. Examples of the filler include powders such as silica and barium sulfate, and fibrous substances such as glass fibers.

[0081] The positive photosensitive resin composition of the present invention can contain a colorant. The colorant is not particularly limited, and known and commonly used colorants such as red, blue, green, yellow, white, black, brown, orange, and purple can be used.

[0082] The positive photosensitive resin composition of the present invention can contain a photo-base generator that is not a covalent bond type within a range that does not impair the effects of the present invention. However, from the viewpoint of efficiently improving the development contrast, it is preferable to suppress the content, and more preferably not to contain it.

[0083] The positive photosensitive resin composition of the present invention may contain a photoacid generator within a range that does not impair the effects of the present invention. However, from the viewpoint of suppressing circuit corrosion, it is preferable to suppress the content, and more preferably not to contain it.

[0084] The positive photosensitive resin composition of the present invention may contain various other organic or inorganic low-molecular or high-molecular compounds. For example, dyes, surfactants, leveling agents, plasticizers, fine particles, etc. can be used. Examples of the fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, and inorganic fine particles such as colloidal silica, carbon, and layered silicates, and they may have a porous or hollow structure. Specific materials for obtaining a porous shape or a hollow structure include various pigments, fillers, and fibers.

[0085] <Dry film> The dry film of the present invention has a resin layer obtained by applying and drying the positive photosensitive resin composition of the present invention on a carrier film (support). The formation of the resin layer is carried out by diluting the photosensitive resin composition of the present invention with a solvent to adjust the viscosity to an appropriate value, and then applying it in a uniform thickness on the carrier film (support film) using a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, spray coater, etc. Thereafter, the applied photosensitive resin composition is usually dried at a temperature of 50 to 130°C for 1 to 30 minutes. The coating film thickness is not particularly limited, but generally, it can be 10 to 150 μm in terms of the film thickness after drying, preferably 20 to 60 μm.

[0086] As the carrier film (support), a plastic film can be used, and examples thereof include polyester films such as polyethylene terephthalate, polyimide films, polyamideimide films, polypropylene films, polystyrene films, etc. The thickness of the carrier film is not particularly limited, but generally, it can be 10 to 150 μm.

[0087] After forming a resin layer composed of the positive photosensitive resin composition of the present invention on the carrier film (support), for the purpose of preventing dust from adhering to the surface of the film, etc., it is preferable to further laminate a peelable protective film (cover film) on the surface of the film. As the peelable protective film (cover film), for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, surface-treated paper, etc. can be used. As the protective film (cover film), it only needs to have an adhesive force smaller than that between the resin layer and the carrier film (support film) when the protective film (cover film) is peeled off.

[0088] <Pattern coating film> The pattern coating film of the present invention can be prepared, for example, as follows.

[0089] [Step 1] The positive photosensitive resin composition of the present invention is applied onto a substrate and dried to obtain a coating film. The coating method is not particularly limited, and for example, methods such as coating with a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., spraying with a spray coater, and inkjet method can be used. The drying method of the coating film is not particularly limited, and methods such as air drying, heat drying with an oven or hot plate, and vacuum drying can be used. Specifically, natural drying, blowing drying, and heat drying under the conditions of 20 to 80 °C for 1 minute to 1 hour can be mentioned. Drying on a hot plate for 1 to 20 minutes is preferred. Also, vacuum drying is possible, and in this case, it can be carried out under the conditions of room temperature for 1 minute to 1 hour.

[0090] The substrate is not particularly limited and can be widely applied to silicon wafers, wiring boards, various resins, metals, passivation protective films of semiconductor devices, etc.

[0091] [Step 2] The coating film formed in Step 1 is exposed through a photomask having a pattern or directly. As the active energy ray used for exposure, those having a wavelength capable of activating the photo-base generator to generate a base can be used, and those having a maximum wavelength in the range of 350 to 410 nm are preferred. The exposure apparatus is not particularly limited, and contact aligners, mirror projections, steppers, laser direct, etc. can be used.

[0092] [Step 3] The coating film exposed in Step 2 is heated to deprotect the protecting groups in the coating film. The heating time and heating temperature can be appropriately adjusted according to the type, amount, and coating film thickness of the polymer of (A) and the covalent photo-base generator of (B), but in the case of a coating film thickness of about 10 μm, it is about 120 to 300 °C for about 30 to 60 minutes.

[0093] [Step 4] The coating film heated in Step 3 is treated with a developer. In the case of a polyimide having a phenolic hydroxyl group protected with a protecting group that is eliminated by the action of a base in the polymer of (A), a patterned coating film can thereby be formed on the substrate.

[0094] The developing method is not particularly limited, and for example, a spin spray method, a paddle method, an immersion method involving ultrasonic treatment, etc. can be used. The developer is not particularly limited, and aqueous solutions of inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, aqueous ammonia, etc., organic amines such as ethylamine, diethylamine, triethylamine, triethanolamine, etc., quaternary ammonium salts such as tetramethylammonium hydroxide, tetrabutylammonium hydroxide, etc. can be used. Also, if necessary, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, isopropyl alcohol, etc. or a surfactant may be added thereto. Thereafter, if necessary, the coating film is washed with a rinse solution to obtain a patterned film. As the rinse solution, distilled water, methanol, ethanol, isopropanol, etc. can be used, and these may be used alone or in any combination of two or more.

[0095] [Step 5] In the case of a polyamic acid having a carboxyl group protected with a protecting group that is eliminated by the action of a base or a polybenzoxazole precursor having a phenolic hydroxyl group protected with a protecting group that is eliminated by the action of a base in the polymer of (A), the film after development obtained in Step 4 is heated to form a patterned coating film that is a cured product of polyimide or polybenzoxazole. The heating temperature can be, for example, 150 to 350 °C, preferably 180 to 300 °C, and the heating time can be, for example, about 5 to 120 minutes. The heating method is not particularly limited, and examples include a hot plate, an oven, a temperature-programmable heating oven, etc. The heating may be carried out under an inert atmosphere or in air, and examples of the inert gas include nitrogen, argon, etc.

[0096] <Use> The use of the positive photosensitive resin composition of the present invention is not particularly limited, and examples thereof include paints, printing inks, adhesives, and the like. The photosensitive resin composition of the present invention can be suitably used as a forming material for display devices, semiconductor elements, electronic components, optical components, building materials, and the like.

[0097] Examples of the forming material for display devices include layer forming materials and image forming materials in color filters, films for flexible displays, resist materials, alignment films, and the like. Examples of the forming material for semiconductor elements include layer forming materials in resist materials, buffer coat films, insulating films for rewiring layers of wafer level packages (WLPs), and the like. Examples of the forming material for electronic components include encapsulating materials and layer forming materials in printed wiring boards, interlayer insulating films, wiring coating films, and the like. Examples of the forming material for optical components include optical materials and layer forming materials in holograms, optical waveguides, optical circuits, optical circuit components, antireflection films, and the like. As building materials, it can be used in paints, coating agents, and the like.

[0098] The positive photosensitive resin composition of the present invention is preferably used as a pattern forming material, particularly for surface protective films, buffer coat films, interlayer insulating films, insulating films for rewiring, protective films for flip chip devices, protective films for devices having bump structures, interlayer insulating films for multilayer circuits, insulating materials for passive components, solder resists, and protective films for printed wiring boards such as coverlay films, liquid crystal alignment films, and the like.

Examples

[0099] The present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. In the following, "parts" and "%" are all based on mass unless otherwise specified.

[0100] The measurements and evaluations in the examples were carried out as follows. <Weight average molecular weight> The weight average molecular weight was measured by gel permeation chromatography (GPC) and converted to a value in terms of standard polystyrene. [Measurement conditions] GPC measurement: GL7700 (GL Science) Columns used: Tosoh TSKgel (registered trademark) α-2500 (φ7.8 mm × 30 cm), α-4000 (φ7.8 mm × 30 cm) Column temperature: 40 °C Eluent conditions: 100 mmol / L H 3 PO 4 , 10 mmol / L LiBr, in NMP Eluent flow rate: 0.5 mL / min Standard reagent for calibration: Polystyrene standard (Showdex) Sample concentration: 0.1% eluent Detector: UV (wavelengths 260 nm and 300 nm), room temperature

[0101] <Development contrast value> The photosensitive resin compositions of the examples and comparative examples were spin-coated on a silicon wafer and pre-baked at 60 °C for 3 minutes. The obtained dry film was irradiated with light of 1000 mJ / cm 2 (365 nm wavelength LED light source) to create exposed and unexposed areas on the film, and then post-exposure heating was performed under the conditions described in Table 1. Development was carried out with a 10% aqueous solution of tetramethylammonium hydroxide, and the development contrast value was calculated from the following formula.

Equation

[0102] <Storage stability of development contrast> The photosensitive compositions of the examples and comparative examples were left standing at 0 °C for one week, and the development contrast was evaluated before and after standing. Those in which the development contrast value did not change before and after standing were marked as ○, those in which the development contrast value changed by 1 to 2 were marked as △, and those in which the development contrast value changed by 2 or more were marked as ×. - indicates that the development contrast value before standing was less than 2 and the measurement after standing was not performed.

[0103] <Resolution> The photosensitive resin compositions of the examples and comparative examples were spin-coated on a silicon wafer and pre-baked at 60 °C for 3 minutes. On the obtained dry film, a mask with L / S (line / space) of 1 μm pitch from 1 μm / 1 μm to 20 μm / 20 μm both in line and space was drawn, and then light irradiation (365 nm wavelength LED light source) of 1000 mJ / cm 2 was performed to create exposed and unexposed areas on the film. After that, post-exposure heating was carried out under the conditions described in Table 1. Development was performed with a 10% aqueous solution of tetramethylammonium hydroxide to obtain a pattern. The minimum line width of the pattern that could be formed was defined as the resolution. Those with a resolution of less than 10 μm were marked as ○, those with a resolution of 10 μm or more and 20 μm or less were marked as △, and those with a resolution of 20 μm or more were marked as ×.

[0104] <Chemical resistance> The photosensitive resin compositions of the examples and comparative examples were spin-coated on a silicon wafer to a dry film thickness of about 3 μm, dried on a hot plate at 100 °C for 5 minutes, and then heated at 180 °C for 1 hour to obtain a cured film. The obtained film was immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide for 1 minute. Those with a reduction rate of less than 5% from the initial film thickness of the cured film were marked as ○, those with a reduction rate of 5% or more and less than 20% were marked as △, and those with a reduction rate of 20% or more were marked as ×.

[0105] Each component used in the examples is as follows. <Synthesis of polyimide (R-1) having phenolic hydroxyl groups> In a eggplant flask, 7.0 g (28 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane (AHPP), which is a diamine, 9.5 g (28 mmol) of 3,3’,4,4’-diphenylsulfone tetracarboxylic dianhydride (also known as 4,4’-[p-sulfonylbis(phenylenesulfanyl)]diphthalic anhydride (DSDA)), which is an acid dianhydride, and 45 ml of dry N-methyl-2-pyrrolidone were added and stirred, and the reaction was carried out at room temperature (23 °C) for 24 hours. 55 ml of dry N-methyl-2-pyrrolidone and 50 ml of toluene were added to the flask, the temperature was raised to 180 °C, and the reaction was carried out for 9 hours. After cooling the reaction solution to room temperature, the polymer was precipitated by dropping it into methanol, and this was filtered and dried to obtain 15 g of the target polyimide (R-1) having a phenolic hydroxyl group and having the following repeating unit. The repeating unit is as follows. When the weight average molecular weight was measured by GPC, it was 1.2×10 4 in terms of polystyrene.

Chemical formula

[0106] <Synthesis of polyimide (A-1) in which the phenolic hydroxyl group is protected by a protecting group> In an eggplant flask, 1.0 g of polyimide (R-1) having a phenolic hydroxyl group, 3.4 g (13 mmol) of 9-fluorenylmethyl chloroformate, 50 ml of dry THF, and 1.3 g (16 mmol) of pyridine were added and stirred, and the reaction was carried out at room temperature for 12 hours. After cooling the reaction solution to room temperature, the polymer was precipitated by dropping it into methanol, and this was filtered and dried to obtain 1.4 g of the target polyimide (A-1) having a repeating unit as shown below and having a phenolic hydroxyl group protected by a protecting group.

Chemical formula

[0107] <Synthesis of polybenzoxazole precursor (A-2) in which the phenolic hydroxyl group is protected by a protecting group> In a flask equipped with a stirrer and a thermometer, 10.0 g (27.3 mmol) of bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), which is a diamine, was stirred and dissolved in 150 ml of dry N-methyl-2-pyrrolidone. Then, the flask was immersed in an ice bath, and while maintaining the temperature inside the flask at 5 °C, 8.78 g (29.8 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride (DEDC) was added, and the mixture was stirred in the ice bath for 30 minutes and then reacted at room temperature for 18 hours. The stirred solution was poured into ion-exchanged water to recover the precipitate. Then, the obtained solid was dissolved in acetone and poured into ion-exchanged water again. The precipitate was recovered and dried to obtain 16 g of a polybenzoxazole precursor (polyhydroxyamide). When the weight-average molecular weight was measured by GPC, it was 2.9×10 4 in terms of polystyrene conversion.

[0108] In an eggplant flask, 1.0 g of a polybenzoxazole precursor (polyhydroxyamide), 3.4 g (13 mmol) of 9-fluorenylmethyl chloroformate, 50 ml of dry THF, and 1.3 g (16 mmol) of pyridine were added and stirred, and the reaction was carried out at room temperature for 12 hours. The reaction solution was dropped into ion-exchanged water to precipitate the polymer, which was then filtered and dried to obtain 1.4 g of a polybenzoxazole precursor (A-2) having the following repeating unit and in which the phenolic hydroxyl group was protected by a protecting group.

Chemical formula

[0109] <Synthesis of polyamic acid (A-3) in which the carboxyl group is protected by a protecting group> In a eggplant flask, 7.0 g (22 mmol) of 2,2'-bis(trifluoromethyl)benzidine (TFMB), which is a diamine, 8.1 g (18 mmol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), which is an acid anhydride, and 81 ml of dry N-methyl-2-pyrrolidone were added and stirred, and reacted at room temperature for 24 hours. The reaction solution was dropped into ion-exchanged water to precipitate the polymer, which was filtered and dried to obtain 13 g of a polyamic acid having a carboxyl group. When the weight-average molecular weight was measured by GPC, it was 1.3×10 4 in terms of polystyrene.

[0110] In a eggplant flask, 1.0 g of a polyamic acid resin having a carboxyl group was dissolved in 10 ml of dry N-methyl-2-pyrrolidone, 0.42 g (3.3 mmol) of oxalyl chloride was dropped, and reacted for 3 hours. 0.23 g (3.3 mmol) of 2-cyanoethanol was dropped into the reaction solution and immersed in an ice bath. After 0.30 g (3.0 mmol) of triethylamine was dropped, it was reacted at room temperature for 16 hours. The reaction solution was dropped into ion-exchanged water to precipitate the polymer, which was filtered and dried to obtain 1.1 g of a polyamic acid resin (A-3) having a carboxyl group protected by a protecting group and having the following repeating unit as the target.

Chemical formula

[0111] <Synthesis of covalent photo-base generator (B-1)> 1.8 g of trans-2-hydroxycinnamic acid, 1.26 g of 1,1,3,3-tetramethylguanidine, and 2.1 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) as a condensing agent were dissolved in tetrahydrofuran (THF) as a solvent and reacted at room temperature for 15 hours. After completion of the reaction, it was diluted with chloroform, and the organic layer was washed in the order of dilute hydrochloric acid, water, and saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate, the solvent was removed, and recrystallization was carried out with chloroform to obtain a compound having the following chemical structure as white crystals. The obtained compound was used as a photo-base generator (B-1).

Chemical Structure

[0112] <Synthesis of Covalent Photo-Base Generator (B-2)> 1.8 g of trans-2-hydroxycinnamic acid, 1.26 g of 2-methyl-2-imidazoline, and 2.1 g of EDC were dissolved in THF as a solvent and reacted at room temperature for 15 hours. After completion of the reaction, it was diluted with chloroform, and the organic layer was washed in the order of dilute hydrochloric acid, water, and saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate, the solvent was removed, and recrystallization was carried out with chloroform to obtain a compound having the following chemical structure as white crystals. The obtained compound was used as a photo-base generator (B-2).

Chemical Structure

[0113] <Synthesis of Covalent Photo-Base Generator (B'-1)> 1.8 g of trans-2-hydroxycinnamic acid, 0.99 g of cyclohexylamine, and 2.1 g of EDC were dissolved in THF as a solvent and reacted at room temperature for 15 hours. After completion of the reaction, it was diluted with chloroform, and the organic layer was washed in the order of dilute hydrochloric acid, water, and saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate, the solvent was removed, and recrystallization was carried out with chloroform to obtain a compound having the following chemical structure as white crystals. The obtained compound was used as a photo-base generator (B'-1). [Chemical formula]

[0114] <Ionic bond type photo-base generator (B'-2)> As the photo-base generator (B'-2), guanidinium 2-(3-benzoylphenyl)propionate (manufactured by Fujifilm Wako Pure Chemical Corporation) was used.

[0115] <Examples> Resins (A-1) to (A-3), (R-1), photo-base generators (B-1) to (B-2), (B'-1) to (B'-2) and a solvent (N,N-dimethylacetamide (DMAc)) were blended at the compounding ratios shown in Table 1 to obtain the photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3. Various measurements were carried out on each photosensitive composition. The results are shown in Table 1.

[0116]

Table 1

[0117] The photosensitive resin compositions of the examples had a large development contrast, excellent resolution, showed good storage stability of the development contrast, and showed good chemical resistance.

Claims

1. (A) a polyimide having a phenolic hydroxyl group protected by a protecting group that is cleaved by the action of a base; (B) a photobase generator obtained by latently bonding a basic compound having a conjugate acid with an acid dissociation constant pKa of 13.0 or more through a covalent bond; Including, The positive-type photosensitive resin composition, wherein the basic compound is 1,5,7-triazabicyclo[4.4.0]dec-5-ene or 1,1,3,3-tetramethylguanidine.

2. (B) is a compound represented by the general formula (1): 【Chemistry 1】 (wherein Z represents an amino group derived from 1,5,7-triazabicyclo[4.4.0]dec-5-ene or an imino group derived from 1,1,3,3-tetramethylguanidine), The positive photosensitive resin composition according to claim 1.

3. (A) is a compound represented by general formula (3): 【Chemistry 2】 ...General formula (3) (where: X ２ is a (4+p)-valent organic group, Y ２ is a (2+q)-valent organic group, R ３ is a protecting group which is removed by the action of a hydrogen atom or a base, and a plurality of R ３ When present, they may be the same or different; R ４ is a protecting group which is removed by the action of a hydrogen atom or a base, and a plurality of R ４ When present, they may be the same or different; p is an integer from 0 to 4; q is an integer from 0 to 4, provided that p and q are not both 0; OR ３ is a ring atom of an aromatic ring; OR ４ is a ring atom of an aromatic ring; R ３ and R ４ Not all of the are hydrogen atoms.) 3. The positive photosensitive resin composition according to claim 1, which comprises a repeating unit represented by the following formula:

4. R ３ The protecting group which is cleaved by the action of a base is a cyanide alkyl group or an alkylazulene group, ４ 4. The positive photosensitive resin composition according to claim 3, wherein the protecting group which is removable by the action of a base is a dialkoxynitrobenzyloxycarbonyl group or a fluorenylmethyloxycarbonyl group.

5. A dry film having a resin layer obtained by applying the positive photosensitive resin composition according to any one of claims 1 to 4 to a film and drying it.

6. A patterned coating film obtained by exposing, heating, developing, and optionally curing the resin layer of the positive photosensitive resin composition according to any one of claims 1 to 4 or the dry film according to claim 5.

7. An electronic component having the pattern coating film according to claim 6.

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