CN115516375A - Positive photosensitive resin composition, dry film, pattern coating film and electronic parts - Google Patents

Abstract

Provides a positive-tone photosensitive resin composition that stably brings about a favorable development contrast. The present invention is a positive photosensitive resin composition comprising: (A) a polyamic acid having a carboxyl group protected by a protecting group detached by the action of a base, and a polyamic acid having a protecting group detached by the action of a base A polyimide with a phenolic hydroxyl group protected by a group or a polybenzoxazole precursor having a phenolic hydroxyl group protected by a protecting group detached from the action of a base; and (B) a photobase generator, the photobase generator Base generators are formed by latent basic compounds with an acid dissociation constant pKa of 10.8 or more through covalent bonds.

Description

Positive photosensitive resin composition, dry film, patterned coating film, and electronic component

technical field

The present invention relates to a positive photosensitive resin composition, a dry film, a patterned coating film, and an electronic component.

Background technique

In recent years, polyimide resins and polybenzoxazole resins have attracted attention as heat-resistant resins excellent in mechanical strength and electrical insulation, and have been widely used as insulating materials for semiconductors and electronic components such as printed circuit boards.

As a method for forming a pattern of polyimide, conventionally, it has been known to use a polyimide precursor having a photosensitive group to form a negative polyimide pattern, but recently it has been proposed that a positive pattern can be realized. Film photosensitive resin composition. As the positive-type photosensitive resin composition, a photoacid generator such as a quinonediazide compound is used, but if the photoacid generator is included, there is a problem that circuits are easily corroded. In this regard, the use of photobase generators has also been tried, and a composition comprising an alkali-soluble resin having a phenolic hydroxyl group, a covalently bonded photobase generator, and an esterification agent for the aforementioned hydroxyl groups has been proposed (Patent Document 1), including A composition of a polyimide resin and a photobase generator in which a phenolic hydroxyl group is protected by a 9-fluorenylmethyloxycarbonyl group (Patent Document 2).

prior art literature

patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2019-45735

Patent Document 2: Japanese Patent Laid-Open No. 2019-194631

Contents of the invention

The problem to be solved by the invention

However, conventional photobase generators sometimes generate bases with low basicity (small acid dissociation constant pKa) and cannot obtain sufficient resolution, and development contrast is required for positive-type photosensitive resin compositions containing photobase generators. further improvement. In addition, it may be seen that the development contrast decreases due to storage, and it is also required to be excellent in stability.

solutions to problems

The present inventors have conducted in-depth research in view of the above, and found that by protecting the carboxyl and phenolic hydroxyl groups in the polymer and combining them with a specific covalent bond type photobase generator, it is possible to give positive photosensitive resins The composition stably brings good development contrast, and thus completed the present invention.

In the composition of the present invention, since the carboxyl group of the polyamic acid, the phenolic hydroxyl group of the polyimide, and the phenolic hydroxyl group of the polybenzoxazole precursor are protected by the protective group released by the action of the base, the unexposed part Alkali solubility is inhibited, and on the other hand, in the exposed part, the protective group is easily detached by the base generated by the specific covalent bond type photobase generator, and alkali solubility is expressed. Due to such a significant difference in alkali solubility between the unexposed part and the exposed part, it is possible to improve the development contrast. In addition, the inventors of the present invention have also found that the development contrast decreases during storage by using a specific covalent bond type photobase generator.

The gist of the present invention is as follows.

[1] A positive photosensitive resin composition comprising:

(A) A polyamic acid having a carboxyl group protected by a protecting group released by the action of a base, a polyimide having a phenolic hydroxyl group protected by a protecting group released by the action of a base, or a polyimide having a carboxyl group protected by a protecting group released by a base The polybenzoxazole precursor of the phenolic hydroxyl group protected by the protecting group released by the effect of

(B) A photobase generator that latently forms a basic compound having an acid dissociation constant pKa of 10.8 or more through a covalent bond.

[2] The positive-type photosensitive resin composition according to [1], wherein (B) is a photobase generator represented by the general formula (1).

(wherein, Z represents an amino group or an imino group.)

[3] The positive-type photosensitive resin composition according to [2], wherein, in the general formula (1), Z is a group represented by the general formula (z1) or a group represented by the general formula (z2) ,

(Wherein, R ₁ and R ₂ are each independently a hydrogen atom or an organic group, R ₁ and R ₂ optionally form a ring structure with the nitrogen atom to which they are bonded, and the ring structure optionally includes other than the aforementioned nitrogen atom heteroatom, _R1 and R2 are not _hydrogen atoms at the same time.)

-N＝CR ₃ R ₄ ... General formula (z2)

(wherein R ₃ and R ₄ are each independently -NR ₅ R ₆ or -C(=O)NR ₇ R ₈ , R ₅ , R ₆ , R ₇ and R ₈ are each independently a hydrogen atom, an alkyl group or Aryl.).

[4] The positive-type photosensitive resin composition according to any one of [1] to [3], wherein (A) contains a repeating unit represented by general formula (2), (3) or (4) ,

(in,

X ¹ is a 4-valent 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 removed by the action of a base, but R ¹ and R ² are not hydrogen atoms at the same time,

X ² is an organic group of (4+p) valence,

Y ² is an organic group of (2+q) valence,

R ³ is a hydrogen atom or a protective group that is removed by the action of a base, and when there are multiple R ³ , they are optionally the same or different,

R ⁴ is a hydrogen atom or a protective group detached by the action of a base, and when there are multiple R ⁴ , they are optionally the same or different,

p is an integer from 0 to 4,

q is an integer from 0 to 4, but p and q are not 0 at the same time,

The carbon atom to which OR ³ is bonded is a ring constituting atom of the aromatic ring,

The carbon atom to which OR ⁴ is bonded is a ring constituting atom of the aromatic ring,

R ³ and R ⁴ are not all hydrogen atoms,

X ³ is a divalent organic group,

Y ³ is an organic group of (2+s) valence,

R ⁵ is a hydrogen atom or a protective group detached by the action of a base, optionally the same or different,

s is an integer from 2 to 8,

The carbon atom to which OR ⁵ is bonded is a ring constituting atom of the aromatic ring,

Not all of R ⁵ are hydrogen atoms. ).

[5] The positive-type photosensitive resin composition according to [4], wherein the protecting group detached by the action of the base of ^R3 is an alkyl cyanide group or an ^alkylazulene group, and the protection group of R4 by the action of the base is ^The protective group detached from the action is dialkoxynitrobenzyloxycarbonyl or fluorenylmethyloxycarbonyl, and the protective group detached from R5 through the action of a base is dialkoxynitrobenzyl Oxycarbonyl or fluorenylmethyloxycarbonyl.

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

[7] A patterned coating film, which is obtained by exposing, heating, and Developed and solidified according to the situation.

[8] An electronic component having the pattern coating film described in [7].

The effect of the invention

According to the present invention, it is possible to provide a positive-type photosensitive resin composition that stably brings good development contrast, a dry film having a resin layer obtained from the composition, a cured product of the resin layer of the composition or a dry film, and a cured product having the resin layer of the composition. Cured semiconductor elements, printed circuit boards and electronic components.

The resin composition of the present invention comprises: (A) a polyamic acid having a carboxyl group protected by a protecting group released by the action of a base, a polyamic acid having a phenolic hydroxyl group protected by a protecting group released by the action of a base. imides or polybenzoxazole precursors having phenolic hydroxyl groups protected by protecting groups that are released by the action of bases; and

(B) A photobase generator that latently forms a basic compound having an acid dissociation constant pKa of 10.8 or more through a covalent bond.

Here, the photobase generator in which a basic compound is latent through a covalent bond refers to a photobase generator in which the generated base is latent using a covalent bond, and the base is generated by irradiation with active energy rays such as light and electromagnetic waves. Alkali agent is a photobase generator of covalent bond type.

<Polymer of (A)>

The polymer of (A) is a polyamic acid having a carboxyl group protected by a protecting group released by the action of a base, a polyimide having a phenolic hydroxyl group protected by a protecting group released by the action of a base, or A polybenzoxazole precursor having a phenolic hydroxyl group protected by a protecting group released by the action of a base. (A) The component may be independent, and may be the combination of arbitrary ratios of 2 or more types.

As a polyamic acid having a carboxyl group protected by a protecting group detached by the action of a base, a polymer having a repeating unit represented by the general formula (2) can be mentioned,

(in,

X ¹ is a 4-valent organic group,

Y ¹ is a divalent organic group,

R ¹ and R ² are each independently a hydrogen atom or a protecting group removed by the action of a base, but R ¹ and R ² are not hydrogen atoms at the same time).

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

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. Examples thereof include the following, but are not limited thereto.

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

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. Examples thereof include the following, but are not limited thereto.

Examples of groups having an aromatic ring include the following, but are not limited thereto.

(wherein, A is a single bond, -CH ₂ -, -O-, -CO-, -S-, -SO ₂ -, -NHCO-, -C(CF ₃ ) ₂ - or -C(CH ₃ ) ₂ -.)

R ¹ and R ² are each independently a hydrogen atom or a protecting group removed by the action of a base, but R ¹ and R ² are not hydrogen atoms at the same time. Both R ¹ and R ² are preferably protecting groups detached by the action of a base, more preferably the same.

The protecting group detached by the action of a base in the general formula (2) is a group protecting a carboxylic acid group, for example, an alkyl cyanide group and an alkylazulene group, and an alkyl cyanide group is preferable. Examples of the alkyl group in these groups include alkyl groups having 1 to 6 carbon atoms. Specific examples of the protecting group detached by the action of a base include the following, but are not limited thereto.

The polymer of the 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 detached by the action of a base into a carboxyl group of the polyamic acid.

As an acid dianhydride, the compound represented by General formula (5) is mentioned.

(Wherein, X ¹ has the same meaning as the general formula (2).)

Examples of acid dianhydrides include 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furyl)naphtho[1,2-c ]furan-1,3-dione, ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane Aliphatic tetracarboxylic dianhydride such as 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 Dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl) base) ether dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl) base) methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexa Fluoropropane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis[(3,4- Dicarboxy)benzoyl]phthalic anhydride, 1,4-bis[(3,4-dicarboxy)benzoyl]phthalic anhydride, 2,2-bis{4-[4-(1,2-di Carboxy)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]biphenyldianhydride, 4,4'-bis[3-(1,2-dicarboxyphenoxy)biphenyldianhydride, 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} Thioether 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-hexafluoropropanedianhydride, 2,3,6 ,7-naphthalene tetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(2,3- or 3,4-dicarboxyphenyl)propane dianhydride, 1 ,4, 5,8-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylene Tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic dianhydride, pyridine tetracarboxylic dianhydride, sulfonyl diphthalic anhydride , m-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3',4,4'-tetracarboxylic dianhydride and other aromatic tetracarboxylic dianhydrides Wait.

Among them, 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furyl)naphtho[1,2-c]furan-1, 3-diketone, 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.

As the acid dianhydride, when an acid dianhydride introduced with fluorine or an acid dianhydride having an alicyclic skeleton is used, good transparency can be maintained and physical properties such as solubility and thermal expansion coefficient can be adjusted.

Examples of diamines that can be used for the preparation of the polymer of general formula (2) are compounds represented by general formula (6).

II ₂ NY ₁ -NII ₂ ...general formula (6)

(Wherein, Y ¹ has the same meaning as the general formula (2).)

Examples of diamines in which Y is ^a divalent aromatic group include p-phenylenediamine, 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'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4 ,4'-Diaminodiphenylsulfoxide, 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, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl Ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene.

Examples of the diamines ^of the divalent aliphatic groups in Y include 1,1-m-xylylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, Hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane , Isophoronediamine, Tetrahydrodicyclopentadienediamine, Hexahydro-4,7-endomethyleneindanylidene dimethylenediamine, Tricyclo[6.2.1.02,7]- Undecyldimethyldiamine, 4,4'-methylenebis(cyclohexylamine), isophoronediamine.

As diamine, the compound represented by General formula (7) can also be used.

(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 1-10. )

Examples of R ₂₈ and R ₂₉ include alkylene groups having 1 to 7 carbons such as methylene, ethylene, and propylene, and arylene groups having 6 to 18 carbons such as phenylene.

Examples of R ₃₀ and R ₃₁ include an alkyl group having 1 to 7 carbons such as a methyl group and an ethyl group, an aryl group having 6 to 12 carbons such as a phenyl group, and the like.

The introduction of a protective group detached by the action of a base into the carboxyl group of the polyamic acid can be carried out by reacting the polyamic acid with R ¹ X or R ² X (where X is a halogen atom, preferably a chlorine atom.) , but not limited to these.

As a polyimide having a phenolic hydroxyl group protected by a protecting group detached by the action of a base, a polymer having a repeating unit represented by the general formula (3) is mentioned,

(in,

X ² is an organic group of (4+p) valence,

Y ² is an organic group of (2+q) valence,

R ³ is a hydrogen atom or a protective group that is removed by the action of a base, and when there are multiple R ³ , they are optionally the same or different,

R ⁴ is a hydrogen atom or a protective group detached by the action of a base, and when there are multiple R ⁴ , they are optionally the same or different,

p is an integer from 0 to 4,

q is an integer from 0 to 4, but p and q are not 0 at the same time,

The carbon atom to which OR ³ is bonded is a ring constituting atom of the aromatic ring,

The carbon atom to which OR ⁴ is bonded is a ring constituting atom of the aromatic ring,

Not all of R ³ and R ⁴ are hydrogen atoms. ).

X ² is an organic group with a valence of (4+p), and the number of carbon atoms in the organic group is preferably 4-40, more preferably 6-34. The organic group preferably has an aromatic ring.

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 are mentioned and p (OR ³ ) groups, but not limited to these.

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

The organic group having an aromatic ring includes groups containing a benzene ring such as a benzene skeleton, a biphenyl skeleton, and a bisphenol skeleton, for example, the following groups and q groups (OR ⁴ ) bonded to them include groups, but not limited to these.

Examples of groups having an aromatic ring include the following, but are not limited thereto.

(wherein, A is a single bond, -CH ₂ -, -O-, -CO-, -S-, -SO ₂ -, -NHCO-, -C(CF ₃ ) ₂ - or -C(CH ₃ ) ₂ -.)

R ³ is a hydrogen atom or a protecting group detached by the action of a base. When there are multiple R ³ , they are optionally the same or different, preferably the same.

R ⁴ is a hydrogen atom or a protective group detached by the action of a base. When there are multiple R ⁴ , they may be the same or different, preferably the same.

p is an integer of 0 to 4, and q is an integer of 0 to 4, but p and q are not 0 at the same time. Preferably (p+q) is an integer of 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.

In general formula (3),

The carbon atom to which OR ³ is bonded is a ring constituting atom of the aromatic ring,

The carbon atom to which OR ⁴ is bonded is a ring constituting atom of the aromatic ring,

Not all of ^R3 and ^R4 are hydrogen atoms, and it is preferable that all of ^R3 and ^R4 are protecting groups detached by the action of a base.

The protective group released by the action of the base in the general formula (3) is a protective group for a phenolic hydroxyl group, for example, mono- or dialkoxynitrobenzyloxycarbonyl, fluorenylmethyloxy ylcarbonyl, preferably fluorenylmethyloxycarbonyl. Specific examples of the protecting group detached by the action of a base include the following, but are not limited thereto.

The polymer of general formula (3) can be prepared as follows, for example, by mixing an acid dianhydride with q phenolic hydroxyl groups and a diamine with p phenolic hydroxyl groups to synthesize a polyamic acid, and making it ring-closed to form a polyimide After the amine, a protective group detached by the action of a base is introduced into the phenolic hydroxyl group in the polyimide.

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

As a diamine which has q phenolic hydroxyl groups, the diamine mentioned in the relationship with the said General formula (2), and the compound which bonded q hydroxyl groups to the aromatic ring of the said diamine are mentioned. For example, examples of diamines having a phenolic hydroxyl group include 2,4-diaminophenol, 3,5-diaminophenol, 2,5-diaminophenol, 1,4-diamino-2,5-diaminophenol, Hydroxybenzene, 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-dihydroxy phenyl)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-hydroxy Phenoxy)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 of the following structures, etc., but are not limited to these.

In order to introduce a protective group detached by the action of a base into the phenolic hydroxyl group of polyimide, it is possible to combine polyimide with R ³ X or R ⁴ X (where X is a halogen atom, preferably a chlorine atom. ) reaction to carry out, but not limited to these.

Examples of the polybenzoxazole precursor having a phenolic hydroxyl group protected by a protecting group released by the action of a base include a polymer having a repeating unit represented by the general formula (4),

(in,

X ³ is a divalent organic group,

Y ³ is an organic group of (2+s) valence,

R ⁵ is a hydrogen atom or a protective group detached by the action of a base, optionally the same or different

s is an integer from 2 to 8,

The carbon atom to which OR ⁵ is bonded is a ring constituting atom of the aromatic ring,

Not all of R ⁵ are hydrogen atoms. ).

^X3 is a divalent organic group, which can be an aliphatic group or an aromatic group, preferably an aromatic group, more preferably bonded to the carbonyl in the general formula (4) on the aromatic ring . The number of carbon atoms in the aromatic group is preferably 6-30, more preferably 6-24.

As an aromatic group, the following are mentioned, for example, but it is not limited to these.

(wherein, A is a single bond, -CH ₂ -, -O-, -CO-, -S-, -SO ₂ -, -NHCO-, -C(CF ₃ ) ₂ - or -C(CH ₃ ) ₂ -.)

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 in the aromatic group is preferably 6-30, more preferably 6-24. More preferably, two (OR ⁵ ) and two amino groups are located in the ortho position on the aromatic ring.

Examples of the aromatic group include the following groups ((OR ⁵ ) bonded to two of the atomic bonds) or (s-2) (OR ⁵ ) bonded to these groups groups, but not limited to these.

R ⁵ is a hydrogen atom or a protecting group detached by the action of a base, which may be the same or different, preferably the same.

s is preferably 2.

In the general formula (4), the carbon atom to which OR ⁵ is bonded is a ring constituting atom of the aromatic ring.

Not all of R ⁵ are hydrogen atoms, and all are preferably protecting groups detached by the action of a base.

The protecting group released by the action of base in the general formula (4) is a group protecting a phenolic hydroxyl group, for example, mono- or dialkoxynitrobenzyloxycarbonyl, fluorenylmethyloxy ylcarbonyl, preferably fluorenylmethyloxycarbonyl. Specific examples of the protecting group detached by the action of a base include the following, but are not limited thereto.

The polymer of the general formula (4) can be produced, for example, by reacting dihydroxydiamine with a dicarboxylic acid halide such as dicarboxylic acid chloride, and introducing a protecting group detached by the action of a base into the phenolic hydroxyl group in the reactant.

As dihydroxydiamine, for example, 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 group)-1,1,1,3,3,3-hexafluoropropane, etc., but are not limited to these. Among them, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane is preferable.

As the dicarboxylic acid in the dicarboxylic acid halide, for example, isophthalic acid, terephthalic acid, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, Formic acid, 5-chloroisophthalic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenyl silane, bis(4-carboxyphenyl)sulfone, 2,2-bis(p-carboxyphenyl)propane, 2,2-bis(4-carboxyphenyl)-1,1,1,3,3,3 -Dicarboxylic acids with aromatic rings such as hexafluoropropane, oxalic acid, malonic acid, succinic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclopentadicarboxylic acid Although aliphatic dicarboxylic acids such as alkanedicarboxylic acid are not limited to these. Among them, 4,4'-dicarboxydiphenyl ether is preferred.

In order to introduce a protective group detached by the action of a base to the phenolic hydroxyl group of the reactant, it is possible to react polyimide with R ³ X or R ⁴ X (where X is a halogen atom, preferably a chlorine atom.) to carry out, but not limited to these.

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

<Specific covalent bond type photobase generator of (B)>

The positive photosensitive resin composition of the present invention contains a photobase generator that latentizes (B) a basic compound having an acid dissociation constant pKa of 10.8 or more through a covalent bond. By containing a specific covalent bond type photobase generator, compared with the case where an ion bond type photobase generator is contained, the dissolution inhibitory effect of an unexposed part becomes favorable, and image development contrast can be improved. In addition, by using a specific covalent bond type photobase generator, it is also possible to suppress a decrease in development contrast during storage.

The acid dissociation constant pKa of the base generated by the covalent bond type photobase generator is preferably 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.

As the generated base, for example, 1,1,3,3-tetramethylguanidine (TMG), dibutylamine (DBA), 1,5,7-triazabicyclo[4.4.0]deca Carb-5-ene (TBD), 2-methyl-2-imidazoline, etc., but not limited to these.

TMG and TBD are preferred.

As the photobase generator, the photobase generator shown in the preferred general formula (1),

(wherein, Z represents an amino group or an imino group.). The amino group or imino group includes the residues of the bases exemplified above.

Z may be a group represented by general formula (z1).

(Wherein, R ₁ and R ₂ are each independently a hydrogen atom or an organic group, R ₁ and R ₂ optionally form a ring structure with the nitrogen atom to which they are bonded, and the ring structure optionally includes other than the aforementioned nitrogen atom heteroatoms, but _R1 and R2 are not _hydrogen atoms at the same time.)

From the viewpoint of the basicity of the base to be generated, R ₁ and R ₂ are preferably both alkyl groups, or form a ring structure together with the nitrogen atom to which they are bonded, and R ₁ and R ₂ form an alkylene group in the ring structure. base chain. The number of carbon atoms constituting the alkyl or alkylene chain is preferably 1-20, more preferably 1-8.

Z can be the group shown in general formula (z2),

-N＝CR ₃ R ₄ ... General formula (z2)

(wherein R ₃ and R ₄ are each independently -NR ₅ R ₆ or -C(=O)NR ₇ R ₈ , R ₅ , R ₆ , R ₇ and R ₈ are each independently a hydrogen atom, an alkyl group or Aryl.). The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, for example, a methyl group or an ethyl group. The aryl group is an aryl group having 6 to 20 carbon atoms, such as a phenyl group and the like. Examples of R ₃ and R ₄ include amino group, mono- or dialkylamino group, phenylamino group, amido group and the like.

Preferably, the following photobase generators are mentioned, but it is not limited to these.

<Compounding amount>

In the positive resin composition of this invention, it is preferable that the covalent bond type photobase generator of (B) is 10-40 mass parts with respect to 100 mass parts of polymers of (A). When it is this range, image development contrast can fully be improved.

<solvent>

The positive photosensitive resin composition of the present invention may contain a solvent, and the solvent is not particularly limited as long as it can dissolve the polymer of (A) and the covalent bond type photobase generator of (B).

Examples of solvents 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-imidazoline Ketone, N-cyclohexyl-2-pyrrolidone, dimethylsulfoxide, hexamethylphosphoramide, pyridine, γ-butyrolactone, diethylene glycol monomethyl ether, etc. These may be used alone, or may be a combination of two or more of them in arbitrary ratios. The amount of the solvent is not particularly limited, and can be adjusted according to coating film thickness, viscosity, and the like, for example. The solvent can be 50-9000 mass parts with respect to 100 mass parts of polymers of (A), for example.

<other ingredients>

The positive photosensitive resin composition of the present invention may contain a sensitizer. By blending a sensitizer, the sensitivity 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'-diethylaminobenzylidene ) cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-dimethylaminobenzylidene)-4-methyl Cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4 '-Bis(diethylamino)chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene) -Benzothiazole, 2-(p-dimethylaminophenylvinylidene)benzothiazole, 2-(p-dimethylaminophenylvinylidene)isonaphthothiazole, 1,3-bis(4' -Dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)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-benzene Diethanolamine, 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-dimethylaminostyrene base) benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, etc., from the aspect of sensitivity , preferably thioxanthones such as 4-(1-methylethyl)-9H-thioxanth-9-one. These may be used alone or in combinations of two or more at arbitrary ratios. A sensitizer can be used, for example at 0.1-10 mass parts with respect to 100 mass parts of polymers of (A).

The positive photosensitive resin composition of the present invention may contain a base multiplying agent. For uniform decomposition of the photobase generator in the film thickness direction, it is preferable to use a base multiplying agent in combination. The base multiplying agent is not particularly limited, and for example, base multiplying agents disclosed in JP-A-2012-237776 and JP-A-2006-282657 can be used.

The positive photosensitive resin composition of the present invention may contain a coupling agent. By compounding a coupling agent, the adhesiveness with a base material improves. The coupling agent is not particularly limited, for example, a silane coupling agent etc. can be mentioned, a silane coupling agent having an alkoxy group, a silane coupling agent having a mercapto group, a silane coupling agent having an epoxy group, a silane coupling agent having Silane coupling agents with ethylenically unsaturated groups, silane coupling agents with arylamino groups, etc. As a commercial item of a coupling agent, the KBM series by Shin-Etsu Silicones company, KBE series, etc. are mentioned, for example. A coupling agent can be used, for example at 0.5-10 mass parts with respect to 100 mass parts of polymers of (A).

The positive photosensitive resin composition of the present invention may contain a melamine-based compound. Chemical resistance improves by compounding a melamine compound. The melamine-based compound is not particularly limited, and examples thereof include MW series manufactured by SANWA Chemical Co., Ltd., and the like.

The positive photosensitive resin composition of the present invention may contain a crosslinking agent having a methylol group. By blending a crosslinking agent having a methylol group, resolution and mechanical properties are improved. For example, TM-BIP-A by Asahi Organic Materials Co., Ltd., TML-BPAF-MF by Honshu Chemical Co., Ltd., etc. are mentioned.

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

The positive photosensitive resin composition of the present invention may contain a colorant. The coloring agent is not particularly limited, and known and commonly used coloring agents such as red, blue, green, yellow, white, black, tea, orange, and purple can be used.

The positive-type photosensitive resin composition of the present invention may contain a photobase generator that is not a covalent bond type within the range that does not impair the effect of the present invention. From the aspect of effective development contrast improvement, it is preferable to suppress the content, and it is more preferable not to contain .

The positive-type photosensitive resin composition of the present invention may contain a photoacid generator within a range not impairing the effects of the present invention. From the viewpoint of suppressing corrosion of circuits, the suppressed content is preferable, and it is more preferable not to contain it.

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

<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 can be carried out by diluting the photosensitive resin composition of the present invention with a solvent to adjust to an appropriate viscosity, and then using a comma coater, a knife coater, a lip coater, Rod coater, extrusion coater, reverse coater, transfer roll coater, gravure coater, spray coater, etc., coat the carrier film (support film) with a uniform thickness, and then apply The 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 usually can be 10 to 150 μm, preferably 20 to 60 μm, as the film thickness after drying.

As the carrier film (support), plastic films can be used, such as polyester films such as polyethylene terephthalate, polyimide films, polyamideimide films, polypropylene films, polystyrene films, etc. film etc. The thickness of the carrier film is not particularly limited, but usually can be set to 10 to 150 μm.

After forming the resin layer formed by the positive photosensitive resin composition of the present invention on the carrier film (support body), for the purpose of preventing dust from adhering to the surface of the film, it is preferable to laminate a peelable protective film on the surface of the film ( cover film). As the peelable protective film (cover film), for example, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc. can be used. The protective film (cover film) should just be smaller than the adhesive force between the resin layer and the carrier film (support film) when the protective film (cover film) is peeled off.

<Pattern coating>

The pattern coating film of this invention can be produced as follows, for example.

[step 1]

A coating film is obtained by applying the positive photosensitive resin composition of the present invention on a base material and drying it. The coating method is not particularly limited, and for example, a coating method using a spin coater, a bar coater, a knife coater, a curtain coater, a screen printing machine, etc., or spray coating using a spray coater can be used. method, inkjet method, etc. The drying method of the coating film is not particularly limited, and methods such as air drying, heat drying with an oven or a hot plate, and vacuum drying can be used. Specific examples include natural drying, air drying, and heat drying at 20 to 80° C. for 1 minute to 1 hour. Drying is preferably performed on a hot plate for 1 to 20 minutes. In addition, vacuum drying may also be used, and in this case, it may be performed at room temperature for 1 minute to 1 hour.

The base material is not particularly limited, and can be widely used in silicon wafers, wiring boards, various resins, metals, passivation protective films of semiconductor devices, and the like.

[step 2]

The coating film formed in step 1 is exposed through a photomask having a pattern or directly. As an active energy ray used for exposure, an active energy ray having a wavelength capable of activating a photobase generator to generate a base can be used, and the maximum wavelength is preferably within a range of 350 to 410 nm. The exposure device is not particularly limited, and a contact photolithography machine, mirror projection exposure machine (mirror projection), stepper, laser direct exposure machine (laser direct), etc. can be used.

[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 and amount of the polymer (A) and the covalent bond type photobase generator (B), and the coating film thickness. In the case of a coating film thickness of about 10 μm , at 120 to 300° C. for about 30 to 60 minutes.

[Step 4]

The coating film heated in step 3 is treated with a developer. When the polymer of (A) is a polyimide having a phenolic hydroxyl group protected by a protecting group detached by the action of an alkali, a patterned coating film can be formed on a base material thereby.

The image development method is not particularly limited, and for example, a rotary spray method, a paddle method, a dipping method with ultrasonic treatment, or the like can be used. The developing solution is not particularly limited, and inorganic bases such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia, organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, tetramethylammonium hydroxide, Aqueous solutions of quaternary ammonium salts such as tetrabutylammonium hydroxide. In addition, an appropriate amount of water-soluble organic solvents such as methanol, ethanol, and isopropanol, and surfactants may be added to these as needed. Thereafter, if necessary, the coating film is washed with a rinse liquid to obtain a patterned film. As the rinsing liquid, distilled water, methanol, ethanol, isopropanol, etc. may be used alone or in any combination of two or more.

[step 5]

The polymer of (A) is a polyamic acid having a carboxyl group protected by a protecting group released by the action of a base or a polybenzoxazole having a phenolic hydroxyl group protected by a protecting group released by the action of a base In the case of a precursor, the developed film obtained in step 4 can be heated to form a pattern coating film that is a cured product of polyimide or polybenzoxazole. The heating temperature can be set to, for example, 150 to 350° C., preferably 180 to 300° C., and the heating time can be set to, for example, about 5 to 120 minutes. The heating method is not particularly limited, and examples thereof include a hot plate, an oven, a temperature-raising oven capable of setting a temperature program, and the like. Heating may be performed in an inert atmosphere or in the air, and examples of the inert gas include nitrogen, argon, and the like.

<purpose>

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.

Examples of the forming material of the display device include layer forming materials and image forming materials such as color filters, films for flexible displays, resist materials, and alignment films.

As a material for forming a semiconductor element, layer forming materials such as a resist material, a buffer coating film, and an insulating film for a rewiring layer of a wafer-level package (WLP) are exemplified.

Examples of forming materials of electronic components include sealing materials and layer forming materials of printed wiring boards, interlayer insulating films, wiring cover films, and the like.

Examples of the forming material of the optical member include optical materials and layer forming materials such as holograms, optical waveguides, optical circuits, optical circuit members, and antireflection films.

As a building material, it can be used in paints, coating agents, etc.

The positive-type photosensitive resin composition of the present invention is preferably used as a pattern forming material, and can be suitably used in particular as a surface protection film, a buffer coating film, an interlayer insulating film, a rewiring Insulating film, protective film for flip-chip devices, protective film for devices with a buffer structure, interlayer insulating film for multilayer circuits, insulating materials for active parts, solder resist and coverlay, etc. for printed circuit boards Protective film, liquid crystal alignment film, etc.

Example

Although the present invention will be described in more detail using examples, the present invention is not limited to the examples. The following "parts" and "%" are all based on mass unless otherwise specified.

Measurements and evaluations in Examples were performed as follows.

<Weight average molecular weight>

The weight average molecular weight is a value measured by gel permeation chromatography (GPC) and converted to standard polystyrene.

[measurement conditions]

GPC determination GL7700 (GLScience company)

α-4000

Column used: Tosoh Corporation TSK gel (registered trademark) α-2500

α-4000

Column temperature: 40°C

Eluent conditions: 100mmol/LH ₃ PO ₄ , 10mmol/LLiBr,inNMP

Eluent flow rate: 0.5mL/min

Calibration standard reagent: polystyrene standard (Showdex company)

Sample concentration: 0.1% eluent

Detector: UV (wavelength 260nm and 300nm), room temperature

<developed contrast value>

The photosensitive resin composition of Example/Comparative Example was spin-coated on a silicon wafer, and pre-baked at 60° C. for 3 minutes. The obtained dried film was irradiated with light of 1000 mJ/cm ² (365 nm wavelength LED light source), and after the exposed part and the unexposed part were formed on the film, post-exposure heating was performed under the conditions described in Table 1. Development was performed with a 10% tetramethylammonium hydroxide aqueous solution, and the development contrast value was computed by the following formula.

The developed contrast value was 5 or more as 0, 2 or more and less than 5 as Δ, and less than 2 as x.

<Storage Stability of Developed Contrast>

The photosensitive composition of the Example and the comparative example was left to stand at 0 degreeC for one week, and the image development contrast evaluation before and after leaving to stand was performed. The case where the development contrast value did not change before and after standing was marked as 0, the case where the development contrast value changed by 1 to 2 was marked as △, and the case where the development contrast value changed by 2 or more was marked as ×. - indicates that the development contrast value before leaving was less than 2, and the measurement after leaving was not performed.

<resolution>

The photosensitive resin composition of Example/Comparative Example was 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/ ^cm2 (365nm wavelength LED light source), after making the exposed part and the unexposed part on the film, under the conditions described in Table 1, perform post-exposure heating. Development was carried out with a 10% tetramethylammonium hydroxide aqueous solution to obtain a pattern.

The minimum line width of a pattern that can be formed is defined as the resolution, 0 is defined as a resolution of less than 10 μm, △ is defined as a resolution of 10 μm or more and 20 μm or less, and × is defined as a resolution of 20 μm or more.

<Chemical Resistance>

The photosensitive resin composition of Example/Comparative Example was spin-coated on a silicon wafer so that the film thickness after drying was about 3 μm, dried on a hot plate at 100° C. for 5 minutes, and then dried at 180° C. By heating for 1 hour, a cured film was obtained. The obtained film was immersed in 2.38% tetramethylammonium hydroxide aqueous solution for 1 minute, and the initial film thickness reduction rate relative to the cured film was less than 5% as 0, and the reduction rate was 5% or more and less than 20%. It was marked as △, and a reduction rate of 20% or more was marked as x.

Each component used in the Example is as follows.

<Synthesis of polyimide (R-1) having phenolic hydroxyl group>

In an eggplant-shaped flask, add 7.0 g (28 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl) propane (AHPP) as diamine, 9.5 g (28 mmol) of 3 ,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (alias: 4,4'-[p-sulfonylbis(phenylenesulfanyl)]diphthalic anhydride (DSDA)] and Dry 45ml of N-methyl-2-pyrrolidone, stir, and react at room temperature (23°C) for 24 hours. Add 55ml of N-methyl-2-pyrrolidone and 50ml of toluene to the flask, and set the temperature to 180°C. 9 hours response.

After the reaction solution was cooled to room temperature, it was added dropwise to methanol to precipitate the polymer, which was filtered and dried to obtain the target polyimide (R-1 ) 15g. The repeating units are as follows.

The weight average molecular weight was measured by GPC and was 1.2×10 ⁴ in terms of polystyrene.

<Synthesis of polyimide (A-1) with phenolic hydroxyl group protected by protecting group>

Add 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 into an eggplant-shaped flask, and stir , reacted at room temperature for 12 hours.

After the reaction solution was cooled to room temperature, it was added dropwise to methanol to precipitate the polymer, which was filtered and dried to obtain the target polyimide having the following repeating unit, in which the phenolic hydroxyl group was protected by a protecting group: Amine (A-1) 1.4 g.

<Synthesis of polybenzoxazole precursor (A-2) with phenolic hydroxyl group protected by protecting group>

In a flask equipped with a stirrer and a thermometer, make 10.0 g (27.3 mmol) of bis(3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP) as a diamine in 150 ml of dry N-methyl-2-pyrrolidone Stir to dissolve. Thereafter, the flask was immersed in an ice bath, the inside of the flask was kept at 5° C., 8.78 g (29.8 mmol) of 4,4′-diphenyl ether diformyl chloride (DEDC) was added, and the reaction was carried out in an ice bath for 30 minutes. Minutes of stirring, room temperature for 18 hours of reaction. The stirred solution was poured into ion-exchanged water, and the precipitate was recovered. Then, the obtained solid was dissolved in acetone, and it poured into ion-exchange water again. The precipitate was recovered and dried to obtain 16 g of a polybenzoxazole precursor (polyhydroxyamide).

The weight average molecular weight was measured by GPC and was 2.9×10 ⁴ in terms of polystyrene.

In an eggplant-shaped flask, add 1.0 g of 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, and stir. The reaction was carried out at room temperature for 12 hours.

The reaction liquid was added dropwise to ion-exchanged water, whereby a polymer was precipitated. This was filtered and dried to obtain 1.4 g of the target polybenzoxazole precursor (A-2) having the following repeating unit and in which the phenolic hydroxyl group was protected with a protecting group.

<Synthesis of Polyamic Acid (A-3) with Carboxyl Group Protected by Protecting Group>

In an eggplant flask, 7.0 g (22 mmol) of 2,2'-bis(trifluoromethyl)benzidine (TFMB) as diamine, 8.1 g (18 mmol) of 4,4'-( Hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 81 ml of dry N-methyl-2-pyrrolidone were stirred and reacted at room temperature for 24 hours. The polymer was precipitated by dropping the reaction liquid into ion-exchanged water, which was filtered and dried to obtain 13 g of polyamic acid having a carboxyl group.

The weight average molecular weight measured by GPC was 1.3×10 ⁴ in terms of polystyrene.

In an eggplant-shaped flask, 1.0 g of 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 added dropwise, and the reaction was carried out for 3 hours. 0.23 g (3.3 mmol) of 2-cyanoethanol was added dropwise to the reaction liquid, and the mixture was immersed in an ice bath. After adding 0.30 g (3.0 mmol) of triethylamine dropwise, the reaction was carried out at room temperature for 16 hours.

The reaction solution was added dropwise to ion-exchanged water to precipitate the polymer, which was filtered and dried to obtain the target polyamic acid resin (A-3) 1.1 having the carboxyl group of the following repeating unit protected by a protecting group g.

<Synthesis of covalent bond type photobase generator (B-1)>

1.8 g of trans-2-hydroxycinnamic acid, 1.26 g of 1,1,3,3-tetramethylguanidine, and 1-ethyl-3-(3-dimethylaminopropyl)carbodiethylene 2.1 g of amine hydrochloride (EDC) was dissolved in tetrahydrofuran (THF), and the reaction was carried out at room temperature for 15 hours. After the reaction was completed, it was diluted with chloroform, and the organic layer was sequentially washed with dilute hydrochloric acid, water, and saturated aqueous sodium bicarbonate solution, dried over anhydrous magnesium sulfate, solvent removed, and recrystallized with chloroform to obtain a white crystal The compound with the following chemical structure is obtained. The obtained compound was used as a photobase generator (B-1).

<Synthesis of covalent bond type photobase 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 the solvent THF, and the reaction was carried out at room temperature for 15 hours. After the reaction was completed, it was diluted with chloroform, and the organic layer was sequentially washed with dilute hydrochloric acid, water, and saturated aqueous sodium bicarbonate solution, dried over anhydrous magnesium sulfate, solvent removed, and recrystallized with chloroform to obtain a white crystal The compound with the following chemical structure is obtained. The obtained compound was used as a photobase generator (B-2).

<Synthesis of covalent bond type photobase 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 the solvent THF, and the reaction was carried out at room temperature for 15 hours. After the reaction was completed, it was diluted with chloroform, and the organic layer was sequentially washed with dilute hydrochloric acid, water, and saturated aqueous sodium bicarbonate solution, dried over anhydrous magnesium sulfate, solvent removed, and recrystallized with chloroform to obtain a white crystal The compound with the following chemical structure is obtained. The obtained compound was used as a photobase generator (B'-1).

<Ion-bonded photobase generator (B'-2)>

As the photobase generator (B'-2), guanidine 2-(3-benzoylphenyl)propionate (manufactured by FUJIFILM Wako Pure Chemical Corporation) was used.

<Example>

Resin (A-1)～(A-3), (R-1), photobase generator (B-1)～(B-2), (B'- 1)-(B'-2) and a solvent (N,N-dimethylacetamide (DMAc)), the photosensitive resin compositions of Examples 1-5 and Comparative Examples 1-3 were obtained. Various measurements were performed for each photosensitive composition. The results are shown in Table 1.

[Table 1]

The photosensitive resin composition of the Example exhibited high development contrast, was excellent in resolution, exhibited favorable storage stability of development contrast, and exhibited favorable chemical resistance.

Claims (8)

1. A positive photosensitive resin composition comprising:

(A) A polyamic acid having a carboxyl group protected with a protecting group which is eliminated by the action of a base, a polyimide having a phenolic hydroxyl group protected with a protecting group which is eliminated by the action of a base, or a polybenzoxazole precursor having a phenolic hydroxyl group protected with a protecting group which is eliminated by the action of a base; and

(B) A photobase generator which comprises a basic compound having an acid dissociation constant pKa of 10.8 or more latent by a covalent bond.

2. The positive photosensitive resin composition according to claim 1, wherein (B) is a photobase generator represented by the general formula (1),

here, Z represents an amino group or an imino group.

3. The positive photosensitive resin composition according to claim 2, wherein in the general formula (1), Z is a group represented by general formula (Z1) or a group represented by general formula (Z2),

wherein R is ₁ And R ₂ Each independently being a hydrogen atom or an organic group, R ₁ And R ₂ Optionally together with the nitrogen atom to which they are bonded, form a cyclic structure optionally containing heteroatoms other than said nitrogen atom, with the proviso that R ₁ And R ₂ Not simultaneously being a hydrogen atom,

-N＝CR ₃ R ₄ \823080general formula (z 2)

Wherein R is ₃ And R ₄ Each independently is-NR ₅ R ₆ or-C (= O) NR ₇ R ₈ ，R ₅ 、R ₆ 、R ₇ And R ₈ Each independently a hydrogen atom, an alkyl group or an aryl group.

4. The positive photosensitive resin composition according to any one of claims 1 to 3, wherein (A) comprises a repeating unit represented by general formula (2), (3) or (4),

wherein,

X ¹ is an organic group having a valence of 4,

Y ¹ is an organic group having a valence of 2,

R ¹ and R ² Each independently a hydrogen atom or a protecting group which is liberated by the action of a base, with the proviso that R is ¹ And R ² Not simultaneously being a hydrogen atom,

X ² is an organic group with valence of (4+p),

Y ² is an organic radical having a valence of (2 q),

R ³ a plurality of R's being present for hydrogen atoms or protecting groups detached by action of a base ³ When they are optionally the same or different,

R ⁴ a plurality of R's being present for hydrogen atoms or protecting groups detached by action of a base ⁴ When they are optionally the same or different,

p is an integer of 0 to 4,

q is an integer of 0 to 4, but p and q are not simultaneously 0,

OR ³ the bonded carbon atom is a ring-constituting atom of an aromatic ring,

OR ⁴ the carbon atom bonded is a ring-constituting atom of an aromatic ring,

R ³ and R ⁴ Not all of them are hydrogen atoms,

X ³ is an organic group having a valence of 2,

Y ³ is an organic group having a valence of (2 + s),

R ⁵ are hydrogen atoms or protecting groups which are liberated by the action of a base, optionally identical or different,

s is an integer of 2 to 8,

OR ⁵ the bonded carbon atom is a ring-constituting atom of an aromatic ring,

R ⁵ not all hydrogen atoms.

5. The positive photosensitive resin set according to claim 4A compound of formula (I), wherein R ³ The protecting group released by the action of a base is an alkyl cyanide or an alkyl azulenyl group, R ⁴ The protecting group released by the action of a base is dialkoxynitrobenzyloxycarbonyl or fluorenylmethyloxycarbonyl, R ⁵ The protecting group to be detached by the action of a base of (a) is a dialkoxynitrobenzyloxycarbonyl group or a fluorenylmethyloxycarbonyl group.

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

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

8. An electronic part having the pattern coating film according to claim 7.