JP2019194631A - Positive type photosensitive resin composition, dry film, pattern coated film, and electronic component - Google Patents

Abstract

To provide a new positive type photosensitive resin composition which can form a positive type pattern coated film having good development contrast without using a photoacid generator; a dry film having a resin layer obtained from the composition; a pattern coated film obtained from the resin layer of the composition or the dry film; and an electronic component having the pattern coated film.SOLUTION: A positive type photosensitive resin composition contains (A) a polyimide resin in which a phenolic hydroxyl group is protected with 9-fluorenylmethyloxycarboxyl group; and (B) a photobase generator.SELECTED DRAWING: None

Description

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

  Polyimide is a heat-resistant resin excellent in mechanical strength and electrical insulation, and is widely applied as an insulating material for electronic parts such as semiconductors and printed wiring boards.

  As a method for forming a polyimide pattern, a method of forming a negative polyimide pattern using a polyimide precursor having a photosensitive group has been known. However, microfabrication is difficult due to high swelling with a developer. Met. In addition, there is a film slip resulting from the elimination of the photosensitive group by the imidization reaction during curing, which may cause deterioration of the pattern. Further, in the negative pattern forming method, it is not easy to form the pattern opening in a reverse taper shape.

  On the other hand, a method of forming a positive polyimide pattern using a composition containing a polyimide precursor soluble in a developing solution such as an alkaline aqueous solution and a photoacid generator such as a quinonediazide compound is known ( For example, Patent Documents 1 to 3). Moreover, the composition containing the polyimide which has the phenolic hydroxyl group which completed imidation reaction previously, and the quinonediazide compound is also proposed (patent document 4). However, when a photoacid generator is included as in the above composition, there is a problem that the circuit is easily corroded.

Japanese Patent Laid-Open No. 2-181149 JP 2000-199958 A Japanese Patent Laid-Open No. 3-115461 Japanese Patent Laid-Open No. 3-177455

  Accordingly, an object of the present invention is to provide a novel positive photosensitive resin composition capable of forming a positive pattern coating film having good development contrast without using a photoacid generator, and a resin obtained from the composition. An object of the present invention is to provide a dry film having a layer, a pattern coating film obtained from the composition or a resin layer of the dry film, and an electronic component having the pattern coating film.

  As a result of intensive studies in view of the above, the present inventors have found that the above problem is solved by using a polyimide resin in which a phenolic hydroxyl group is protected with a 9-fluorenylmethyloxycarbonyl group (Fmoc group) and a photobase generator. As a result, the present invention has been completed.

  That is, the positive photosensitive resin composition of the present invention includes (A) a polyimide resin in which a phenolic hydroxyl group is protected with a 9-fluorenylmethyloxycarbonyl group, and (B) a photobase generator. It is characterized by.

  The dry film of the present invention is characterized by having a resin layer obtained by applying and drying the positive photosensitive resin composition on a film.

  The patterned coating film of the present invention is obtained by exposing, heating, and developing the positive photosensitive resin composition or the resin layer of the dry film.

  The electronic component of the present invention has the pattern coating film.

  According to the present invention, a novel positive photosensitive resin composition capable of forming a positive pattern coating film with good development contrast without using a photoacid generator, and a resin layer obtained from the composition are provided. It is possible to provide a dry film having, a pattern coating film obtained from the composition or a resin layer of the dry film, and an electronic component having the pattern coating film.

  According to the positive photosensitive resin composition of the present invention, (A) a polyimide resin (hereinafter referred to as “Fmoc group”) in which a phenolic hydroxyl group is protected with a 9-fluorenylmethyloxycarbonyl group (hereinafter also referred to as “Fmoc group”). (A) also referred to as “polyimide resin”), the phenolic hydroxyl group, which is an alkali-soluble group, is protected with an Fmoc group, so that the alkali solubility is inhibited in the unexposed area. On the other hand, the exposed portion is subjected to a certain amount of heat treatment as a post-bake in the presence of a base generated from a photobase generator, so that (A) the phenolic hydroxyl group of the polyimide resin is deprotected and alkali solubility is exhibited. I found. In the present invention, it is possible to form a positive pattern by photolithography using the difference in alkali solubility between the unexposed area and the exposed area.

  Since the positive photosensitive resin composition of the present invention does not need to contain a photoacid generator as described above, it is possible to suppress the occurrence of circuit corrosion that becomes a problem when a photoacid generator is used. It becomes. Further, since the positive photosensitive resin composition of the present invention can form a positive pattern, the shape of the opening has an inverse taper and can be suitably used as a semiconductor interlayer insulating material. In addition, a reverse taper shape means the shape where the deep part (board | substrate side) became thicker than the surface in the cross section of the pattern of a coating film.

  Furthermore, since the positive photosensitive resin composition of the present invention contains a ring-closed imide, it does not require a high-temperature treatment usually exceeding 300 ° C., which is performed to cause an imidation reaction of the precursor, and has no high-temperature resistance. It can also be suitably used for coating.

  In the composition of Patent Document 4, a polyimide having a phenolic hydroxyl group is used, but the temperature is gradually increased from 90 to 400 ° C. after development in order to improve thermal stability such as decomposition of the photoacid generator. It was necessary to raise the temperature, and there was a concern about solvent resistance because the phenolic hydroxyl group remained after heating. On the other hand, the positive photosensitive resin composition of the present invention does not need to be heated at such a high temperature and is excellent in chemical resistance (also referred to as chemical resistance) because the phenolic hydroxyl group is protected. A coated film can be obtained.

  Hereinafter, the components contained in the positive photosensitive resin composition of the present invention will be described in detail.

[(A) Polyimide resin in which phenolic hydroxyl group is protected with 9-fluorenylmethyloxycarbonyl group]
The positive photosensitive resin composition of the present invention contains (A) a polyimide resin in which a phenolic hydroxyl group is protected with a 9-fluorenylmethyloxycarbonyl group (Fmoc group). (A) The polyimide resin is not particularly limited as long as the phenolic hydroxyl group of the polyimide resin having a phenolic hydroxyl group is protected with an Fmoc group. For protecting the phenolic hydroxyl group by the Fmoc group, a known and conventional method may be used. For example, Fmoc-Cl is reacted with fluorenylmethyl chloroformate (Fmoc-Cl) in the presence of a base such as pyridine or triethylamine. It can be protected with a group.

  (A) A polyimide resin may be used individually by 1 type, and may be used in combination of 2 or more type. The compounding amount of the resin is preferably 30 to 90% by mass, and more preferably 40 to 90% by mass based on the total solid content of the composition excluding the solvent.

  Although the polyimide resin which has a phenolic hydroxyl group is not specifically limited, As a specific example, the polyimide resin which has a repeating unit represented by following General formula (1) is mentioned.

(Wherein R ₁ represents an organic group having at least 2 carbon atoms, R ₂ represents an organic group having at least 2 carbon atoms, and p and q are each an integer from 0 to 4) (However, p + q> 0, and the carbon atom of the partner to which the hydroxyl group is covalently bonded is a carbon atom that forms part of the aromatic ring.)

  The OH group (hydroxyl group) described in the above formula (1) is a phenolic hydroxyl group because it is covalently bonded to a carbon atom forming a part of the aromatic ring. Examples of the aromatic ring include a benzene ring and a naphthalene ring.

In the above formula (1), R ₁ is not particularly limited as long as it is an organic group that can be bonded to four carbonyl groups and p OH groups. Similarly, R ₂ is not particularly limited as long as it is an organic group that can be bonded to two amines and q OH groups.

The organic group represented by R ₁ may not have an aromatic ring when p is 0, but has an aromatic ring when p is any integer from 1 to 3. The number of carbon atoms of the organic group represented by R ₁ is preferably 4 to 40, more preferably 6 to 34.

Examples of R ₁ include a group containing an aromatic ring, preferably a group containing an aromatic ring having 6 to 34 carbon atoms. R ₁ is preferably a polybasic acid residue. Here, the group containing an aromatic ring is preferably a group having a skeleton containing a benzene ring such as a benzene skeleton, a biphenyl skeleton, or a bisphenyl skeleton. Specific examples of the group containing an aromatic ring include the following tetravalent groups and groups in which any hydrogen atom of the following tetravalent groups is substituted with an OH group, but are not limited thereto. Absent.

The organic group represented by R ₂ may not have an aromatic ring when q is 0, but has an aromatic ring when q is any integer from 1 to 3. The number of carbon atoms of the organic group represented by R ₂ is preferably 4 to 40, more preferably 6 to 34.

Examples of R ₂ include a group containing an aromatic ring, preferably a group containing an aromatic ring having 6 to 34 carbon atoms. R ₂ is preferably a diamine residue having a phenolic hydroxyl group. Here, the group containing an aromatic ring is preferably a group having a skeleton containing a benzene ring such as a benzene skeleton, a biphenyl skeleton, or a bisphenyl skeleton. Specific examples of the group containing an aromatic ring include the following divalent groups and groups in which any one of the following divalent groups has a hydrogen atom substituted with an OH group, but are not limited thereto. Absent.

(In the formula, A is a single bond, —CH ₂ —, —O—, —CO—, —S—, —SO ₂ —, —NHCO—, —C (CF ₃ ) ₂ —, —C (CH ₃ ). ₂ represents a divalent group selected from the group consisting of 2-.

  In said formula (1), it is preferable that p is 0-2. q is preferably from 0 to 2. p + q is preferably from 1 to 4, more preferably 1 or 2.

  (A) The preferable weight average molecular weight of a polyimide resin is 1000-1 million, it is preferable that it is 5000-100,000, and it is more preferable that it is 10,000-50,000.

  The method for obtaining a polyimide resin having a phenolic hydroxyl group is not particularly limited. Usually, it is obtained by reacting and polymerizing a polybasic acid or its derivative and a diamine, preferably by ring-closing a polyimide precursor obtained by reacting and polymerizing a tetracarboxylic acid or its derivative and a diamine, in particular, In general, a polyimide precursor obtained by reacting and polymerizing a tetracarboxylic dianhydride (hereinafter abbreviated as an acid anhydride) and a diamine is closed to obtain.

  As the diamine, for example, when q in the formula (1) is 1 to 3, a diamine having a phenolic hydroxyl group may be used, and when q is 0, a diamine having no phenolic hydroxyl group may be used. Good. The said diamine can be used 1 type or in mixture of 2 or more types.

  The diamine having a phenolic hydroxyl group is not particularly limited, but specific examples thereof 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-dihydroxy) Phenyl) 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, '-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- Ruboxy-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, diamine having the following structure, and the like are preferable, but are not limited thereto.

  The diamine having no phenolic hydroxyl group is not particularly limited, but specific examples thereof include 4,4′-methylene-bis (2,6-ethylaniline), 4,4′-methylene-bis (2- Isopropyl-6-methylaniline) 4,4′-methylene-bis (2,6-diisopropylaniline), 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl- 1,4-phenylenediamine, o-tolidine, m-tolidine, 3,3 ′, 5,5′-tetramethylbenzidine, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4 -(3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 4,4'-diamino-3,3'-dimethyldi Cyclohexylmethane, 4,4′-diaminodiphenyl ether, 3,4-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 2,2-bis (4-anilino) hexafluoropropane, 2,2-bis (3-anilino) Hexafluoropropane, 2,2-bis (3-amino-4-toluyl) hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, bis [ 4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, etc. Can be mentioned. (A) From the viewpoint of solubility of the polyimide resin, 4,4′-methylene-bis (2,6-ethylaniline), 4,4′-methylene-bis (2-isopropyl-6-methylaniline), 4 , 4′-methylene-bis (2,6-diisopropylaniline), bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2, 2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane and the like are preferable, but are not limited thereto. Moreover, (A) The siloxane containing diamine is preferable from the point of the adhesiveness of a polyimide resin.

  Examples of the tetracarboxylic acid include tetravalent butane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, Examples thereof include hydroxypyromellitic acid, dihydroxybenzophenone tetracarboxylic acid, trihydroxybenzophenone tetracarboxylic acid, and tetrahydroxybenzophenone tetracarboxylic acid.

  Specific examples of tetracarboxylic dianhydrides applicable to the synthesis of a polyimide resin having a phenolic hydroxyl group include ethylene tetracarboxylic dianhydride and 1,2,3,4-butanetetracarboxylic dianhydride. 1,2,3,4-cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1, 2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5- Cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic acid dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6 Tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 3 , 5,6-tricarboxy-2-norbornane acetic acid dianhydride, cycloaliphatic tetracarboxylic dianhydride such as 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5- Aliphatic tetracarboxylic dianhydrides such as dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione; 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'-Biff Niltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3 ′, 3,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 6 , 6′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3 , 3 ′, 4,4′-diphenylsulfonetetracarboxylic 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 Anhydride, 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 , Screw {4- [4- (1,2-dica Boxy) phenoxy] phenyl} ketone dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, 4,4′-bis [4- (1,2-di) Carboxy) 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 Anhydride, 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 1,2,4,5-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 And aromatic tetracarboxylic dianhydrides such as p-terphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride and tetracarboxylic dianhydrides having the following structure. .

  Among the tetracarboxylic anhydrides, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride are considered from the viewpoint of solubility. 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride and the like are preferable.

  These polybasic acids or their derivatives and diamines can be used alone or in combination of two or more.

  To synthesize a polyimide resin having a phenolic hydroxyl group from tetracarboxylic dianhydride and diamine, the polyimide precursor is reacted with tetracarboxylic dianhydride and diamine in a polar solvent such as N-methylpyrrolidone or dimethylacetamide. A method of synthesizing a body and dehydrating and closing a ring is common.

  The reaction temperature of tetracarboxylic dianhydride and diamine can be selected from -20 to 150 ° C, preferably -5 to 100 ° C.

  In order to convert the polyimide precursor to a polyimide resin, the polyimide precursor is heated in a solution state at 150 to 250 ° C. Toluene or xylene is added to remove water generated by dehydration ring closure. It is also possible to perform dehydration by boiling.

  Further, as a simpler method for converting a polyimide precursor into a polyimide resin, there is catalytic imidation.

  For example, a tertiary amine such as triethylamine, pyridine, isoquinoline, or imidazole is added to the polyimide precursor solution, and imidization is performed at an arbitrary temperature of 0 to 250 ° C., or an acid such as acetic acid is added to the polyimide precursor solution. The imidization can be performed at an arbitrary temperature of 0 to 250 ° C.

  Moreover, the polyimide resin having a phenolic hydroxyl group may be obtained by reacting tetracarboxylic dianhydride with diisocyanate.

[(B) Photobase generator]
The positive photosensitive resin composition of the present invention contains (B) a photobase generator. Here, the photobase generator is a base generator that generates a base upon irradiation with electromagnetic waves, in which the generated base is latent. By containing the photobase generator, the unexposed part is insoluble in the alkali solution due to the dissolution inhibiting effect by the Fmoc group, and the exposed part becomes excellent in solubility in the alkaline solution by the elimination of the Fmoc group, A positive pattern can be formed.

  The photobase generator may be an ionic photobase generator or a non-ionic photobase generator, but the ionic photobase generator has a higher composition sensitivity and is advantageous for forming a pattern film. This is preferable. Examples of basic substances include secondary amines and tertiary amines.

  Examples of ionic photobase generators include salts of aromatic component-containing carboxylic acids and tertiary amines, and WPBG-082, WPBG-167, WPBG-168, and WPBG- ionized PBG manufactured by Wako Pure Chemical Industries, Ltd. 266, WPBG-300, or the like can be used.

  Nonionic photobase generators include, for example, α-aminoacetophenone compounds, oxime ester compounds, N-formylated aromatic amino groups, N-acylated aromatic amino groups, nitrobenzyl carbamate groups, alcoholoxybenzyls. Examples thereof include compounds having a substituent such as a carbamate group. Other photobase generators include WPBG-018 (trade name: 9-anthrylmethyl N, N'-diethylcarbamate), WPBG-027 (trade name: (E) -1- [3- (2 -Hydroxyphenyl) -2-propenoyl] piperidine), WPBG-140 (trade name: 1- (anthraquinon-2-yl) ethyl imidazolecarboxylate), WPBG-165, and the like can also be used.

  (B) As for the compounding quantity of a photobase generator, 10-40 mass parts is preferable with respect to 100 mass parts of (A) polyimide resin in which the phenolic hydroxyl group was protected by 9-fluorenylmethyloxycarbonyl group. It becomes easy to obtain contrast as it is 10-40 mass parts.

  Below, the other component which can be mix | blended with the positive photosensitive resin composition of this invention is demonstrated.

  Solvents that can be used in the positive photosensitive resin composition of the present invention are (A) a polyimide resin in which a phenolic hydroxyl group is protected with a 9-fluorenylmethyloxycarbonyl group, and (B) a photobase generator. There is no particular limitation as long as it can be used. Examples include N, N′-dimethylformamide, N-methylpyrrolidone (NMP), N-ethyl-2-pyrrolidone, N, N′-dimethylacetamide, 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 be able to. These may be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited. For example, depending on the coating film thickness and viscosity, (A) 100 parts by mass of the polyimide resin in which the phenolic hydroxyl group is protected with a 9-fluorenylmethyloxycarbonyl group, What is necessary is just to use in the range of 50-9000 mass parts.

  A sensitizer can also be added to the positive photosensitive resin composition of the present invention in order to further improve the photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzal) cyclopentane, and 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-di Tilaminophenylvinylene) 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, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, dimethylaminobenzoic acid Amyl, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benz Examples include thiazole, 2- (p-dimethylaminostyryl) naphtho (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, and 4- (1-methylethyl)-in terms of sensitivity. It is preferable to use thioxanthones such as 9H-thioxanthen-9-one. These can be used alone or in combination of 2 to 5 kinds. The sensitizer is preferably used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of (A) a polyimide resin in which a phenolic hydroxyl group is protected with a 9-fluorenylmethyloxycarbonyl group.

  A base proliferating agent may be added to the positive photosensitive resin composition of the present invention. When forming a thick film pattern, the decomposition rate of the same amount of photobase generator is required from the surface to the bottom. In this case, in order to improve sensitivity, the addition of a base proliferating agent is preferable. For example, it is possible to use a base proliferating agent disclosed in JP 2012-237776 A, JP 2006-282657 A, or the like.

  A coupling agent may be blended in the positive photosensitive resin composition of the present invention. By blending the coupling agent, the adhesion to the substrate is improved. A coupling agent is not specifically limited, For example, a silane coupling agent etc. are mentioned. Examples of the silane coupling agent include a silane coupling agent having an alkoxy group, a silane coupling agent having an amino group, a silane coupling agent having a mercapto group, a silane coupling agent having an epoxy group, and an ethylenically unsaturated group. And a silane coupling agent having an arylamino group. Examples of commercially available coupling agents include, for example, KBM series and KBE series manufactured by Shin-Etsu Silicone. The blending amount of the coupling agent is preferably in the range of 0.5 to 10 parts by mass with respect to 100 parts by mass of (A) a polyimide resin in which the phenolic hydroxyl group is protected with a 9-fluorenylmethyloxycarbonyl group.

  You may mix | blend a melamine type compound with the positive photosensitive resin composition of this invention. Chemical resistance improves by mix | blending a melamine type compound. The melamine compound is not particularly limited, and examples thereof include MW series manufactured by Sanwa Chemical Co., Ltd.

  You may mix | blend a filler with the positive photosensitive resin composition of this invention. A filler is not specifically limited, Any of an inorganic filler and an organic filler may be sufficient. Examples of the filler include powders such as silica and barium sulfate, and fibrous substances such as glass fibers.

  You may mix | blend a coloring agent with the positive photosensitive resin composition of this invention. 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.

  As described above, the positive photosensitive resin composition of the present invention can form a positive pattern without blending a photoacid generator. The positive photosensitive resin composition of the present invention may contain a photoacid generator as long as the effects of the present invention are not impaired, but from the viewpoint of suppressing circuit corrosion, It is preferably not contained, and preferably 0 to 20% by mass, more preferably 0 to 10% by mass, and still more preferably 0% by mass based on the total solid content of the composition excluding the solvent.

  The positive photosensitive resin composition of the present invention may contain an epoxy compound, but it is not necessary to contain an epoxy compound as in the photosensitive resin composition described in, for example, International Publication WO2016 / 052493. If it contains an epoxy compound, it may react with the phenolic hydroxyl group and hinder the solubility of the exposed area, so even if it is contained, it is preferable to contain a small amount or not, and the solid content of the composition excluding the solvent It is preferably 0 to 10% by mass based on the total amount, more preferably 0 to 3% by mass, and further preferably 0% by mass.

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

  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 dry film is formed by diluting the positive photosensitive resin composition of the present invention with the above-mentioned organic solvent and adjusting the viscosity to an appropriate viscosity, followed by a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, and a reverse coater. Apply to uniform thickness on carrier film with transfer roll coater, gravure coater, spray coater, etc. Then, the resin layer can be formed by drying the applied photosensitive resin composition usually at a temperature of 50 to 130 ° C. for 1 to 30 minutes. Although there is no restriction | limiting in particular about a coating film thickness, Generally, it is 10-150 micrometers by the film thickness after drying, Preferably it selects suitably in the range of 20-60 micrometers.

  As the carrier film, a plastic film is used, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is preferably used. Although there is no restriction | limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 10-150 micrometers.

  After the resin layer made of the positive photosensitive resin composition of the present invention is formed on the carrier film, a cover that can be peeled off on the surface of the film for the purpose of preventing dust from adhering to the surface of the film. It is preferable to laminate films. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used. As a cover film, what is necessary is just a thing smaller than the adhesive force of a resin layer and a carrier film when peeling a cover film.

  Next, the manufacturing method of the pattern coating film using the positive photosensitive resin composition of this invention is demonstrated.

  First, as Step 1, a positive photosensitive resin composition is applied onto a substrate and dried to obtain a coating film. As a method for applying the positive photosensitive resin composition on the substrate, methods conventionally used for applying the photosensitive resin composition, for example, spin coater, bar coater, blade coater, curtain coater, screen printing, etc. A coating method using a machine, a spray coating method using a spray coater, an ink jet method or the like can be used. As a method for drying the coating film, methods such as air drying, heat drying with an oven or hot plate, and vacuum drying are used. Specifically, natural drying, air drying, or heat drying can be performed at 20 to 80 ° C. for 1 minute to 1 hour. Preferably, drying is performed on a hot plate for 1 to 20 minutes. Moreover, vacuum drying is also possible, and in this case, it can be performed at room temperature for 1 minute to 1 hour.

  There is no restriction | limiting in particular in a base material, It can apply widely to the passivation protective film of a silicon wafer, a wiring board, various resin, a metal, a semiconductor device, etc.

  In addition, unlike the case of using a polyimide precursor as an alkali-soluble resin, the positive photosensitive resin composition of the present invention does not need to be imidized after application, so that it can be used for high-temperature processing of printed wiring board substrates and the like. It is characterized by being widely applicable to unsuitable members and materials.

  Next, as the step 2, the coating film is exposed through a photomask having a pattern or directly. The exposure light having a wavelength capable of activating the photobase generator to generate a base is used. As described above, the photosensitivity can be adjusted by appropriately using a sensitizer. As the exposure apparatus, a contact aligner, mirror projection, stepper, laser direct exposure apparatus, or the like can be used.

  Subsequently, in step 3, heating is performed so as to deprotect the Fmoc group of the polyimide resin having a phenolic hydroxyl group protected with the Fmoc group in the coating film. The heating time and heating temperature are appropriately changed depending on the polyimide resin to be used, the type of photobase generator, and the coating film thickness. Typically, in the case of a coating film thickness of about 10 μm, it is about 30 to 60 minutes at 120 to 300 ° C.

  Next, in step 4, the coating film is treated with a developer. Thereby, a pattern coating film can be formed on a base material.

As a method used for the development, an arbitrary method can be selected from conventionally known photoresist development methods such as a rotary spray method, a paddle method, and an immersion method involving ultrasonic treatment. Developers include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide. An aqueous solution of quaternary ammonium salts such as Further, if necessary, a water-soluble organic solvent such as methanol, ethanol, isopropyl alcohol, or a surfactant can be used in an appropriate amount as an aqueous solution. Thereafter, the coating film is washed with a rinse liquid as necessary to obtain a pattern film. As the rinsing liquid, distilled water, methanol, ethanol, isopropanol or the like can be used alone or in combination.

  The use of the positive photosensitive resin composition of the present invention is not particularly limited. For example, printing ink, adhesive, filler, electronic material, optical circuit component, molding material, resist material, building material, three-dimensional modeling, optical Examples include various known fields and products in which resin materials are used, such as members. In particular, a wide range of fields and products in which the properties of polyimide film such as heat resistance, dimensional stability, and insulation are effective, such as paints or printing inks, color filters, films for flexible displays, and coating films for semiconductor elements It is suitably used as a coating material for printed wiring boards such as electronic parts, interlayer insulating films, solder resists, optical circuits, optical circuit parts, antireflection films, holograms, optical members or building materials.

  In particular, the positive photosensitive resin composition of the present invention is mainly used as a pattern forming material (resist), and a pattern film formed thereby imparts heat resistance and insulation as a permanent film made of polyimide. Electronic components such as color filters, flexible display films, insulating materials for passive components, coating films for semiconductor elements, interlayer insulating films, coating films for printed wiring boards such as solder resists and coverlay films It is suitable for forming coating films, solder dams, optical circuits, optical circuit components, antireflection films, other optical members or electronic members.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to the following Example. In the following description, “parts” and “%” are all based on mass unless otherwise specified.

<Synthesis of Polyimide Resin R-1 Having Phenolic Hydroxyl Group>
In an eggplant flask, 1.60 parts of 2,2-bis (3-amino-4-hydroxyphenyl) propane (hereinafter abbreviated as AHPP), which is a diamine, 2.20 parts of 3,3 ′, which is an acid anhydride, 4,4′-diphenylsulfonetetracarboxylic dianhydride (also known as 4,4 ′-[p-sulfonylbis (phenylenesulfanyl)] diphthalic anhydride (hereinafter abbreviated as DPSDA)] and dry N-methyl-2-pyrrolidone After adding 24 parts, the mixture was stirred and allowed to react at room temperature for 24 hours, 3.7 parts of dry toluene was further added to the flask, and the temperature was raised to 180 ° C. for 10 hours.
The reaction solution was cooled to room temperature and then dropped into methanol to precipitate a polymer, which was filtered and dried to obtain 2.1 parts of a polyimide resin having a desired phenolic hydroxyl group.
When the weight average molecular weight was measured by GPC, it was 10000 in terms of polystyrene, and Mw / Mn = 1.1.
The obtained resin was dissolved in heavy DMSO and subjected to 1H-NMR measurement. The hydrogen content derived from methyl group was 1.54 ppm, the 12 hydrogen content derived from the aromatic ring was 6.8-8.6 ppm, and 9.62 ppm. A 2 hydrogen signal derived from a phenolic hydroxyl group was observed, confirming that the structure was the target.

<Confirmation of imidization rate>
To dissolve 0.05 parts of the resin obtained above in 0.4 parts of THF, apply a spin coat method on a silicon substrate and dry at 60 ° C., and to completely imidize for reference A thin film heated at 300 ° C. for 1 hour was prepared.
As a result of confirming the degree of imidation by comparing the intensity of SO ₂ -derived peak (1325 cm ⁻¹ ) with the peak of imide C—N (1380 cm ⁻¹ ) intensity by FT-IR measurement, it was dried at 60 ° C. 95% or more was imidized at the stage of the treatment.
Moreover, since the obtained thin film was completely dissolved when immersed in an aqueous 2.5% by weight tetramethylammonium hydroxide solution for 30 seconds, the obtained resin had a phenolic hydroxyl group having the following structural unit. It was ring-closing polyimide resin R-1.

<Synthesis of polyimide resin (A) in which phenolic hydroxyl group is protected with Fmoc group>
In an eggplant flask, 1.9 parts of R-1 which is a polyimide resin having a phenolic hydroxyl group, 3.7 parts of 9-fluorenylmethyl chloroformate, 60 parts of dry THF and 1.2 parts of pyridine were added and stirred. And allowed to react at room temperature for 24 hours.
Separately, 520 g of ion-exchanged water is prepared in a beaker, and a methanol diluted reaction solution is dropped into the well-stirred exchanged water to precipitate a polymer, which is filtered and dried to obtain the following structural unit. Obtained 1.9 parts of polyimide resin (A). When the weight average molecular weight was measured by GPC, it was 16000 in terms of polystyrene and Mw / Mn = 3.5.

<Synthesis of polyimide resin R-2 in which phenolic hydroxyl group is protected with acetal group>
In an eggplant flask, 1.9 parts of R-1 which is a polyimide resin having a phenolic hydroxyl group, 3.7 parts of cyclohexanedimethanol divinyl ether, 60 parts of dry THF and 1.2 parts of pyridine were added and stirred at room temperature. The reaction was performed for 24 hours.
Separately, 520 g of ion-exchanged water is prepared in a beaker, and the polymer diluted by dropping the methanol-diluted reaction solution into the well-exchanged water is filtered, dried and filtered to obtain the desired polyimide resin R-2. 1.9 parts of was obtained. When the weight average molecular weight was measured by GPC, it was 15000 in terms of polystyrene, and Mw / Mn = 3.2.

(Examples 1 and 2 and Comparative Examples 1 to 4)
Polyimide resins (A), polyimide resins R-1, R-2, and ionic photobase generators (B) in which the phenolic hydroxyl groups are protected with Fmoc groups at the compounding ratios (mass ratios) shown in Table 1 below. -1, Covalent Photobase Generator (B) -2 and Tetrahydrofuran were blended, and the performance of each composition of Examples and Comparative Examples was evaluated. The photobase generator includes ionic type (B) -1: guanidinium 2- (3-benzoylphenyl) propionate manufactured by Wako Pure Chemical Industries, Ltd. (WPBG-082 manufactured by Wako Pure Chemical Industries, Ltd.), and covalent bond type (B). -2: (E) -1-piperidino-3- (2-hydroxyphenyl) -2-propen-1-one (WPBG-027 manufactured by Wako Pure Chemical Industries, Ltd.)) was used.

(Development contrast)
Each of the above compositions was spin-coated on a hydrophobized silicon wafer and dried at 60 ° C. for 3 minutes to obtain a film. The obtained dried film was irradiated with light of 40,000 mJ / cm ² using a 365 nm wavelength LED light source (illuminance 50 mW / cm ² ). The film after irradiation is subjected to a heat treatment for 30 minutes on a hot plate at a predetermined temperature described in the table, and developed with a 5.0% by weight aqueous solution of tetramethylammonium hydroxide for each development time. The remaining amount of the film in the unexposed area and the exposed area was measured, and the development contrast value was calculated by the following formula.
A development contrast value of 5 or more was defined as ◎, 2.6 or more and less than 5 as ◯, 1.5 or more and less than 2.6 as Δ, and less than 1.5 as x.

(Chemical resistance)
Each of the above compositions was spin coated on a silicon wafer to a thickness of 2 μm after drying, dried on a hot plate at 100 ° C. for 5 minutes, and then heated at 180 ° C. for 1 hour to obtain a film. The obtained film was immersed in an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by weight for 40 seconds, and the change in film thickness was unchanged from the initial film thickness or the decrease was less than 5%. A case where the amount was 5% or more and less than 20% was evaluated as “◯”, a case where the reduction rate was 20% or more and less than 80%, “Δ”, and a case where the amount decreased by 80% or more was evaluated as “X”.

(B-HAST test)
Each of the above compositions was applied onto a comb / tooth electrode having a line / space = 6/6 μm and dried, and then the comb-tooth substrate was placed on a HAISTAME MODEL PC-R8D manufactured by HIRAYAMA which was set to a temperature of 130 ° C. and a humidity of 85%. In the B-HAST test in which a voltage of 5.5 V was applied, the insulation resistance value was observed even after 100 hours had elapsed. A resistance value of 10 ⁸ or more was evaluated as ◎, a resistance value of 10 ⁶ or more and less than 10 ⁸ was evaluated as Δ, and a resistance value of less than 10 ⁶ was evaluated as x.

  From the results shown in Table 1, it can be seen that according to the positive photosensitive resin composition of the present invention, it is possible to form a positive putter coating film having good development contrast without using a photoacid generator.

Claims (4)

(A) a polyimide resin in which a phenolic hydroxyl group is protected with a 9-fluorenylmethyloxycarbonyl group;
(B) A positive photosensitive resin composition comprising a photobase generator.   A dry film comprising a resin layer obtained by applying and drying the positive photosensitive resin composition according to claim 1 on a film.   A pattern coating film obtained by exposing, heating, and developing the resin layer of the positive photosensitive resin composition according to claim 1 or the dry film according to claim 2.   An electronic component comprising the pattern coating film according to claim 3.