CN112771447A - Positive photosensitive resin composition, photosensitive resin film using the same, and electronic device - Google Patents

Positive photosensitive resin composition, photosensitive resin film using the same, and electronic device Download PDF

Info

Publication number
CN112771447A
CN112771447A CN201980063779.2A CN201980063779A CN112771447A CN 112771447 A CN112771447 A CN 112771447A CN 201980063779 A CN201980063779 A CN 201980063779A CN 112771447 A CN112771447 A CN 112771447A
Authority
CN
China
Prior art keywords
chemical formula
photosensitive resin
unsubstituted
substituted
resin composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201980063779.2A
Other languages
Chinese (zh)
Inventor
权志伦
姜真熙
金度煜
权章玄
金尚洙
金二柱
白宅晋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Samsung SDI Co Ltd
Original Assignee
Samsung SDI Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Samsung SDI Co Ltd filed Critical Samsung SDI Co Ltd
Publication of CN112771447A publication Critical patent/CN112771447A/en
Pending legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)

Abstract

The present invention provides: a positive photosensitive resin composition comprising (a) an alkali-soluble resin, (B) a photosensitive diazoquinone compound, (C) a compound represented by a specific chemical formula, and (D) a solvent; a photosensitive resin film produced using the same; and an electronic device including the photosensitive resin film.

Description

Positive photosensitive resin composition, photosensitive resin film using the same, and electronic device
Technical Field
The present disclosure relates to a positive photosensitive resin composition, and a photosensitive resin film and an electronic device using the same.
Background
Polyimide resins, polybenzoxazole resins and the like having improved heat resistance, electrical characteristics and mechanical characteristics have been widely used for surface protective layers and interlayer insulating layers used in materials for display device panels and semiconductor devices. Because these resins have low solubility in various solvents, they are generally provided as compositions in which their precursors are dissolved in solvents.
In recent years, due to recent increase in environmental problems, countermeasures against organic solvents are required, and heat-resistant photosensitive resin materials that can be developed with an alkaline aqueous solution in the same manner as photoresists have been proposed.
Among them, a method using a photosensitive resin composition comprising a mixture of a hydroxypolyamide resin and a photoacid generator (such as a naphthoquinone diazide compound) which are soluble in an alkaline aqueous solution as a heat-resistant resin after heat curing has been proposed.
The mechanism of photosensitivity of the photosensitive resin composition is to use exposure of a photosensitive diazoquinone compound to a naphthoquinone diazide compound (i.e., a photosensitive diazoquinone (diazoquinone) compound) and a Polybenzoxazole (PBO) precursor in an unexposed portion, and thereby convert the photosensitive diazoquinone compound into an indenecarboxylic acid (indenecarboxylic acid) compound to increase the dissolution rate in an alkaline aqueous solution. The difference in dissolution rate between exposed and unexposed portions can be used to produce a relief pattern composed of unexposed portions.
The photosensitive resin composition may form a positive relief pattern by exposure and development with an aqueous alkaline solution. Further, the heat-cured film characteristics can be obtained by heating.
However, in the manufacturing process of semiconductors and the like, fine processing is performed and the intervals between patterns become shorter. For this reason, when the film reduction amount becomes large, in an unexposed portion adjacent to an exposed portion of the opening, the dissolution rate of the unexposed portion is small, but is in contact with the developing solution from one side of the film and from the upper side of the film during development, and thereby, the shape of the pattern becomes too thin, deteriorating the reliability of the semiconductor package in the manufacturing process of the semiconductor device.
Therefore, it is necessary to develop the unexposed portion almost without dissolving the unexposed portion (this phenomenon is called a developing film remaining rate). However, when the developing film residual rate increases, the phenomenon of the exposed portion requires a high exposure dose (this is called low sensitivity).
Therefore, a method of adding a phenolic compound to a heat-resistant resin precursor has been proposed as a method of increasing the film residual ratio during development (developability control) and the development sensitivity. However, the conventionally used phenolic compounds have limitations in improving sensitivity and film residue rate, and in addition, there is a problem that scum occurs when improving sensitivity or film residue rate.
Therefore, research into developing positive photosensitive resin compositions capable of solving the problems is continued.
Disclosure of Invention
[ problem ] to
One embodiment provides a positive photosensitive resin composition capable of improving a film residue rate and sensitivity without generating scum.
Another embodiment provides a photosensitive resin film manufactured using the positive photosensitive resin composition.
Another embodiment provides an electronic device including a positive photosensitive resin film.
[ solution ]
One embodiment provides a positive photosensitive resin composition comprising (a) an alkali soluble resin; (B) a photosensitive diazoquinone compound; (C) a compound represented by chemical formula 1; and (D) a solvent.
[ chemical formula 1]
Figure BDA0002994901960000021
In the chemical formula 1, the first and second,
R1is a hydrogen atom, or a substituted or unsubstituted C1 to C20 alkyl group,
R2and R3Independently is a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group, and
n is an integer of 0 or 1.
Chemical formula 1 may be represented by chemical formula 1-1 or chemical formula 1-2.
[ chemical formula 1-1]
Figure BDA0002994901960000031
[ chemical formulas 1-2]
Figure BDA0002994901960000032
In chemical formula 1-1 and chemical formula 1-2,
R4is a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group,
R5is unsubstituted C1 to C20 alkyl,
R6is a substituted or unsubstituted C1 to C20 alkyl group, and
n is an integer of 0 or 1.
The chemical formula 1-1 may be represented by one of chemical formulas 1-1-1 to 1-1-3.
[ chemical formula 1-1-1]
Figure BDA0002994901960000033
[ chemical formulas 1-1-2]
Figure BDA0002994901960000034
[ chemical formulas 1-1-3]
Figure BDA0002994901960000041
In chemical formulas 1-1-1 to 1-1-3,
R7is a substituted or unsubstituted C1 to C20 alkoxy group,
R8is a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group, and
R9is-CRaRbRc(wherein, Ra、RbAnd RcIndependently is a substituted or unsubstituted C1 to C10 alkyl group, provided that Ra、RbAnd RcAt least one of which is different from the other two).
The chemical formula 1-2 may be represented by chemical formula 1-2-1 or chemical formula 1-2-2.
[ chemical formula 1-2-1]
Figure BDA0002994901960000042
[ chemical formula 1-2-2]
Figure BDA0002994901960000043
In chemical formula 1-2-1 and chemical formula 1-2-2,
R5is unsubstituted C1 to C20 alkyl, and
R10is a substituted or unsubstituted C1 to C20 alkyl group.
The compound represented by chemical formula 1 may be represented by one of chemical formula 1A to chemical formula 1F.
[ chemical formula 1A ]
Figure BDA0002994901960000051
[ chemical formula 1B ]
Figure BDA0002994901960000052
[ chemical formula 1C ]
Figure BDA0002994901960000053
[ chemical formula 1D ]
Figure BDA0002994901960000054
[ chemical formula 1E ]
Figure BDA0002994901960000055
[ chemical formula 1F ]
Figure BDA0002994901960000056
The compound represented by chemical formula 1 may be included in an amount of 0.5 to 40 parts by weight based on 100 parts by weight of the alkali soluble resin.
The alkali soluble resin may comprise a polybenzoxazole precursor, a polyimide precursor, a phenolic resin, or a combination thereof.
The positive photosensitive resin composition may further include a crosslinking agent.
The photosensitive resin composition may include 5 to 50 parts by weight of the photosensitive diazoquinone compound, 0.5 to 40 parts by weight of the compound represented by chemical formula 1, and 100 to 500 parts by weight of the solvent, based on 100 parts by weight of the alkali-soluble resin.
The photosensitive resin composition may further include the following additives: a dibasic acid, an alkanolamine, a leveling agent, a silane-based coupling agent, a surfactant, an epoxy compound, a free radical polymerization initiator, a thermal latent acid generator, or a combination thereof.
Another embodiment provides a photosensitive resin film prepared by using the photosensitive resin composition.
Another embodiment provides an electronic device including a positive photosensitive resin film.
Other embodiments of the invention are included in the following detailed description.
[ advantageous effects ]
The positive photosensitive resin composition according to an embodiment includes a compound having a specific structure, thereby improving sensitivity and a film residue rate without generating scum, and thus may be usefully used to manufacture a circuit protection layer used in an electronic device such as a semiconductor device.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. However, these embodiments are exemplary, the present invention is not limited thereto, and the present invention is defined by the scope of the claims.
In the present specification, when a specific definition is not otherwise provided, "alkyl" means C1 to C20 alkyl, "alkenyl" means C2 to C20 alkenyl, "cycloalkenyl" means C3 to C20 cycloalkenyl, "heterocycloalkenyl" means C3 to C20 heterocycloalkenyl, "aryl" means C6 to C20 aryl, "aralkyl" means C6 to C20 aralkyl, "alkylene" means C1 to C20 alkylene, "arylene" means C6 to C20 arylene, "alkylenearyl (alkylarylene group)" means C6 to C20 alkylenearyl, "heteroarylene (heteroarylene group)" means C3 to C20 heteroarylene, and "alkyleneoxy" means C1 to C20 alkyleneoxy.
In the present specification, when a specific definition is not otherwise provided, "substituted" means that at least one hydrogen is replaced by a substituent selected from the group consisting of halogen (F, Cl, Br, or I), hydroxyl group, C1 to C20 alkoxy group, nitro group, cyano group, amine group, imino group, azide group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamoyl group, thiol group, ester group, ether group, carboxyl group or a salt thereof, sulfonic acid group or a salt thereof, phosphoric acid group or a salt thereof, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C20 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, C2 to C20 heterocycloalkyl group, C2 to C20 heterocycloalkenyl group, C2 to C20 heterocycloalkynyl group, C3 to C30 heteroaryl group, or a combination thereof.
In the present specification, when a specific definition is not otherwise provided, "hetero" refers to at least one hetero atom including N, O, S and P in the chemical formula.
In the present specification, "(meth) acrylate" means "acrylate" and "methacrylate" when a specific definition is not otherwise provided.
In the present specification, "combination" means mixing or copolymerization when a definition is not otherwise provided. Further, "copolymerization" means block copolymerization, alternating copolymerization, or random copolymerization, and "copolymer" means a block copolymer, alternating copolymer, or random copolymer.
In the present specification, when a specific definition is not otherwise provided, the unsaturated bond includes a bond between other atoms (such as a carbonyl bond or an azo bond) and a multiple bond between carbon-carbon atoms.
In the present specification, when a definition is not otherwise provided, hydrogen bonding is at a position in the chemical formula where the chemical bond is supposed to be given but not drawn.
In addition, in the present specification, "_ represents a connection point having the same or different atom or chemical formula when no definition is otherwise provided.
A photosensitive resin composition according to an embodiment includes: (A) an alkali-soluble resin; (B) a photosensitive diazoquinone compound; (C) a compound represented by chemical formula 1; and (D) a solvent.
[ chemical formula 1]
Figure BDA0002994901960000071
In the chemical formula 1, the first and second,
R1is a hydrogen atom,Or a substituted or unsubstituted C1 to C20 alkyl group,
R2and R3Independently is a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group, and
n is an integer of 0 or 1.
The positive photosensitive resin composition according to an embodiment uses a compound represented by chemical formula 1, which has both polar and non-polar groups, as a dissolution control agent, thereby improving film-remaining rate and sensitivity without damaging a pattern. Further, while minimizing film reduction of the exposed portions, unexposed portions do not leave scum and dissolve well in an alkaline developing solution. The effect in terms of quantity and quality is improved compared to the properties seen with conventional dissolution control agents.
Hereinafter, each component is explained in detail.
(C) A compound represented by chemical formula 1
The compound represented by chemical formula 1 may be represented by chemical formula 1-1 or chemical formula 1-2.
[ chemical formula 1-1]
Figure BDA0002994901960000081
[ chemical formulas 1-2]
Figure BDA0002994901960000082
In chemical formula 1-1 and chemical formula 1-2,
R4is a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group,
R5is unsubstituted C1 to C20 alkyl,
R6is a substituted or unsubstituted C1 to C20 alkyl group, and
n is an integer of 0 or 1.
The chemical formula 1-1 may be represented by one of chemical formulas 1-1-1 to 1-1-3.
[ chemical formula 1-1-1]
Figure BDA0002994901960000083
[ chemical formulas 1-1-2]
Figure BDA0002994901960000091
[ chemical formulas 1-1-3]
Figure BDA0002994901960000092
In chemical formulas 1-1-1 to 1-1-3,
R7is a substituted or unsubstituted C1 to C20 alkoxy group,
R8is a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group, and
R9is-CRaRbRc(wherein, Ra、RbAnd RcIndependently is a substituted or unsubstituted C1 to C10 alkyl group, provided that Ra、RbAnd RcAt least one of which is different from the other two).
The chemical formula 1-2 may be represented by chemical formula 1-2-1 or chemical formula 1-2-2.
[ chemical formula 1-2-1]
Figure BDA0002994901960000093
[ chemical formula 1-2-2]
Figure BDA0002994901960000094
In chemical formula 1-2-1 and chemical formula 1-2-2,
R5is unsubstituted C1 to C20 alkyl, and
R10is a substituted or unsubstituted C1 to C20 alkyl group.
For example, the compound represented by chemical formula 1 may be represented by one of chemical formula 1A to chemical formula 1F, but is not limited thereto.
[ chemical formula 1A ]
Figure BDA0002994901960000101
[ chemical formula 1B ]
Figure BDA0002994901960000102
[ chemical formula 1C ]
Figure BDA0002994901960000103
[ chemical formula 1D ]
Figure BDA0002994901960000104
[ chemical formula 1E ]
Figure BDA0002994901960000105
[ chemical formula 1F ]
Figure BDA0002994901960000111
The amount of the compound represented by chemical formula 1 is desirably 0.5 to 40 parts by weight, for example, 1 to 30 parts by weight, based on 100 parts by weight of the alkali-soluble resin. When the amount of the compound represented by chemical formula 1 is within the above range, the dissolution rate and sensitivity of the exposed portion may be increased when developed with an aqueous alkaline solution, and high-resolution patterning may be performed without a development residue (scum) during development.
(A) Alkali soluble resin
The alkali soluble resin is a resin including a hydroxyl group, such as a polybenzoxazole precursor, a polyimide precursor, a (cresyl) phenol resin, a bisphenol a resin, a bisphenol F resin, a (meth) acrylate resin, or a combination thereof.
The polybenzoxazole precursor may include a structural unit represented by chemical formula 2, and the polyimide precursor may include a structural unit represented by chemical formula 3.
[ chemical formula 2]
Figure BDA0002994901960000112
In the chemical formula 2, the first and second organic solvents,
X0and X1Independently a substituted or unsubstituted C6 to C30 aromatic organic radical,
Y0and Y1Independently a substituted or unsubstituted C6 to C30 aromatic organic radical, a substituted or unsubstituted divalent to hexavalent C1 to C30 aliphatic organic radical, or a substituted or unsubstituted divalent to hexavalent C3 to C30 cycloaliphatic organic radical,
Rxand RyIndependently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a metal ion, or an ammonium ion, and
m1 and m2 are each independently an integer of 0 to 100,000, provided that m1+ m2 is an integer greater than or equal to 2.
[ chemical formula 3]
Figure BDA0002994901960000121
In the chemical formula 3, the first and second,
X2is a substituted or unsubstituted C6 to C30 aromatic organic radical, a substituted or unsubstituted divalent to hexavalent C1 to C30 aliphatic organic radical, or a substituted or unsubstituted divalent to hexavalent C3 to C30 cycloaliphatic organic radical, and
Y2is a substituted or unsubstituted C6 to C30 aromatic organic radical, a substituted or unsubstituted tetravalent to hexavalent C1 to C30 aliphatic organic radical, or a substituted or unsubstituted tetravalent to hexavalent C3 to C30 alicyclic organic radical.
In chemical formula 2, X1May be a moiety derived from an aromatic diamine as the aromatic organic group.
Examples of the aromatic diamine may be at least one selected from the following compounds: 3,3 '-diamino-4, 4' -dihydroxybiphenyl, 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-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3, 3-hexafluoropropane, 2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3, 3-hexafluoropropane, 2-bis (3-amino-4-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2, 2-bis (3-amino-4-hydroxy-6-trifluoromethylphenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxy-2-trifluoromethylphenyl) hexafluoropropane, 2-bis (4-amino-3-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2-bis (4-amino-3-hydroxy-6-trifluoromethylphenyl) hexafluoropropane, 2-bis (4-amino-3-hydroxy-2-trifluoromethylphenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxy-5-pentafluoroethylphenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-5-trifluoromethylphenyl) hexafluoropropane 2- (3-amino-4-hydroxy-5-pentafluoroethylphenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-5-trifluoromethylphenyl) -2- (3-hydroxy-4-amino-5-trifluoromethylphenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-5-trifluoromethylphenyl) -2- (3-hydroxy-4-amino-6-trifluoromethylphenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-5-trifluoromethylphenyl) -2- (3-hydroxy-4-amino-2-trifluoromethylphenyl) hexafluoropropane, and, 2- (3-amino-4-hydroxy-2-trifluoromethylphenyl) -2- (3-hydroxy-4-amino-5-trifluoromethylphenyl) hexafluoropropane and 2- (3-amino-4-hydroxy-6-trifluoromethylphenyl) -2- (3-hydroxy-4-amino-5-trifluoromethylphenyl) hexafluoropropane, but are not limited thereto.
X0And X1Embodiments of (1) may include the functional group represented by chemical formula 4 or chemical formula 5, but are not limited thereto.
[ chemical formula 4]
Figure BDA0002994901960000131
[ chemical formula 5]
Figure BDA0002994901960000132
In chemical formula 4 and chemical formula 5,
A1may be a single bond, O, CO, CR47R48、SO2Or S, wherein R47And R48Independently a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group, specifically a C1 to C30 fluoroalkyl group,
R50to R52May independently be a hydrogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 carboxyl group, a hydroxyl group, or a mercapto group,
n10 is an integer from 0 to 2, and n11 and n12 are independently integers from 0 to 3.
In chemical formula 2, Y0And Y1May independently be part of a dicarboxylic acid or part of a dicarboxylic acid derivative as an aromatic organic radical, a divalent to hexavalent aliphatic organic radical or a divalent to hexavalent cycloaliphatic organic radical. Specifically, Y0And Y1May be an aromatic organic radical, or a divalent to hexavalent cycloaliphatic organic radical.
Specific examples of the dicarboxylic acid derivative may be 4,4' -oxybenzoyl chloride, diphenoxydicarbonyl dichloride, bis (phenylcarbonyl chloride) sulfone, bis (phenylcarbonyl chloride) ether (bis (phenylcarbonyl chloride) ether), bis (phenylcarbonyl chloride) phenone, phthaloyl dichloride, terephthaloyl dichloride, isophthaloyl dichloride, dicarbonyl dichloride, diphenoxydicarboxylate dibenzotriazole (diphenoxydicarbonyl dicarboxylate) or a combination thereof, but are not limited thereto.
Y0And Y1Embodiments of (1) may include functional groups represented by chemical formulas 6 to 8, but are not limited thereto.
[ chemical formula 6]
Figure BDA0002994901960000133
[ chemical formula 7]
Figure BDA0002994901960000141
[ chemical formula 8]
Figure BDA0002994901960000142
In chemical formulas 6 to 8,
R53to R56Independently a hydrogen atom, or a substituted or unsubstituted C1 to C30 alkyl group,
n13and n14Independently is an integer of 0 to 4, n15 and n16 independently are an integer of 0 to 3, and
A2is a single bond, O, CR47R48CO, CONH, S, or SO2Wherein R is47And R48Independently a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group, specifically a C1 to C30 fluoroalkyl group.
In chemical formula 3, X2May be an aromatic organic radical, a divalent to hexavalent aliphatic organic radical, or a divalent to hexavalent cycloaliphatic organic radical. Specifically, X2May be an aromatic organic radical or a divalent to hexavalent cycloaliphatic organic radical.
Specifically, X2May be a residue derived from an aromatic diamine, an alicyclic diamine, or a silicon diamine. In this case, the aromatic diamine, the alicyclic diamine and the silicon diamine may beUsed alone or in combination of one or more.
Examples of the aromatic diamine may be 3, 4' -diaminodiphenyl ether, 4' -diaminodiphenyl ether, 3, 4' -diaminodiphenylmethane, 4' -diaminodiphenylsulfone, 4' -diaminodiphenyl sulfide, benzidine, m-phenylenediamine, p-phenylenediamine, 1, 5-naphthalenediamine, 2, 6-naphthalenediamine, bis [4- (4-aminophenoxy) phenyl ] sulfone, bis (3-aminophenoxy phenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl ] ether, 1, 4-bis (4-aminophenoxy) benzene, a compound having an aromatic ring substituted with an alkyl group or a halogen atom, or a combination thereof, but is not limited thereto.
Examples of the alicyclic diamine may include 1, 2-cyclohexyl diamine, 1, 3-cyclohexyl diamine, or a combination thereof, but are not limited thereto.
Examples of the silicon diamine include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (p-aminophenyl) tetramethyldisiloxane, bis (γ -aminopropyl) tetramethyldisiloxane, 1, 4-bis (γ -aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (γ -aminopropyl) tetraphenyldisiloxane, 1, 3-bis (aminopropyl) tetramethyldisiloxane, or a combination thereof, but are not limited thereto.
In chemical formula 3, Y2May be an aromatic organic group, a tetravalent to hexavalent aliphatic organic group, or a tetravalent to hexavalent alicyclic organic group. Specifically, Y2May be an aromatic organic radical, or a tetravalent to hexavalent cycloaliphatic organic radical.
Y2May be a moiety derived from an aromatic acid dianhydride or an alicyclic acid dianhydride. In this case, the aromatic acid dianhydride and the alicyclic acid dianhydride may be used alone or in combination of one or more.
Examples of the aromatic acid dianhydride may include: pyromellitic dianhydride; benzophenone tetracarboxylic dianhydrides such as benzophenone-3, 3', 4,4' -tetracarboxylic dianhydride; oxydiphthalic dianhydrides, such as 4,4' -oxydiphthalic dianhydride; biphenyl dicarboxylic acid dianhydrides such as 3,3', 4,4' -biphenyl dicarboxylic acid dianhydride; (hexafluoroisopropylidene) diphthalic dianhydrides, such as 4,4' - (hexafluoroisopropylidene) diphthalic dianhydride; naphthalene-1, 4,5, 8-tetracarboxylic dianhydride; 3,4,9, 10-perylenetetracarboxylic dianhydride, and the like, but is not limited thereto.
Examples of the alicyclic acid dianhydride may include 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 5- (2, 5-dioxotetrahydrofuryl) -3-methyl-cyclohexane-1, 2-dicarboxylic anhydride, 4- (2, 5-dioxotetrahydrofuryl-3-yl) -tetrahydronaphthalene-1, 2-dicarboxylic anhydride, bicyclooctene-2, 3,5, 6-tetracarboxylic dianhydride, bicyclooctene-1, 2,4, 5-tetracarboxylic dianhydride, etc., but are not limited thereto.
For example, the alkali soluble resin may comprise a polybenzoxazole precursor, a polyimide precursor, a phenolic resin, or a combination thereof.
For example, the alkali soluble resin may comprise a polybenzoxazole precursor and a (cresol-based) phenolic resin. When both the polybenzoxazole precursor and the (cresyl) phenol resin are contained, it may be advantageous to control the development rate and form a fine pattern.
The alkali-soluble resin may have a weight average molecular weight (Mw) of 3,000 to 300,000g/mol, and specifically, may have a weight average molecular weight (Mw) of 5,000 to 30,000 g/mol. In the case where the weight average molecular weight (Mw) is within the above range, when developed with an aqueous alkaline solution, a sufficient film residual ratio can be obtained in the unexposed portion, and patterning can be performed efficiently.
(B) Photosensitive diazoquinone compound
The photosensitive diazoquinone compound may be a compound having a 1, 2-benzoquinone diazide structure or a 1,2 naphthoquinone diazide structure.
Examples of the photosensitive diazoquinone compound may be compounds represented by chemical formula 9 and chemical formulae 11 to 13, but are not limited thereto.
[ chemical formula 9]
Figure BDA0002994901960000161
In the chemical formula 9, the first and second,
R31to R33May independently be a hydrogen atom or a substituted or unsubstituted alkyl group, in particular CH3，
D1To D3May be independently OQ, wherein Q may be a hydrogen atom, a functional group represented by chemical formula 10a, or a functional group represented by chemical formula 10b, provided that Q is not simultaneously a hydrogen atom, and
n31 to n33 are independently integers from 1 to 5.
[ chemical formula 10a ]
Figure BDA0002994901960000162
[ chemical formula 10b ]
Figure BDA0002994901960000163
[ chemical formula 11]
Figure BDA0002994901960000171
In the chemical formula 11, the first and second,
R34may be a hydrogen atom or a substituted or unsubstituted alkyl group,
D4to D6May be independently OQ, wherein Q is the same as defined in chemical formula 9, and
n34 to n36 are independently integers from 1 to 5.
[ chemical formula 12]
Figure BDA0002994901960000172
In the chemical formula 12, the first and second,
A3may be CO or CR500R501Wherein R is500And R501Can be independently usedAnd is either a substituted or unsubstituted alkyl group,
D7to D10May be independently a hydrogen atom, a substituted or unsubstituted alkyl group, OQ, or NHQ, wherein Q is the same as defined in chemical formula 9,
n37, n38, n39 and n40 may be independently integers of 1 to 4, and
n37+ n38 and n39+ n40 may independently be integers less than or equal to 5,
provided that D is7To D10Is OQ, and one aromatic ring contains 1 to 3 OQ, and the other aromatic ring contains 1 to 4 OQ.
[ chemical formula 13]
Figure BDA0002994901960000173
In the chemical formula 13, the first and second carbon atoms are represented by,
R35to R42May independently be a hydrogen atom or a substituted or unsubstituted alkyl group,
n41 and n42 may independently be integers of 1 to 5, specifically 2 to 4, and
q is the same as defined in chemical formula 9.
The photosensitive diazoquinone compound may desirably be included at 5 to 50 parts by weight, for example, 10 to 40 parts by weight, based on 100 parts by weight of the alkali-soluble resin. When the content of the photosensitive diazoquinone compound is within the above range, pattern formation by exposure is well performed without residue, there is no loss of film thickness during development, and a good pattern can be obtained.
(D) Solvent(s)
The photosensitive resin composition may include a solvent capable of easily dissolving each component, such as an alkali-soluble resin, a photosensitive diazoquinone compound, and a compound represented by chemical formula 1.
The solvent may be an organic solvent, specifically, N-methyl-2-pyrrolidone, γ -butyrolactone, N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1, 3-butanediol acetate, 1, 3-butanediol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, or the like, or a combination thereof, but is not limited thereto.
The solvent may be appropriately selected according to a process of forming a photosensitive resin film such as spin coating, slit die coating (slit die coating), or the like.
The solvent may be used in an amount of 100 to 500 parts by weight, for example, 100 to 300 parts by weight, based on 100 parts by weight of the alkali-soluble resin. When the solvent is used within this range, a film having a sufficient thickness can be obtained, and the solubility and coating property can be improved.
Crosslinking agent
The positive photosensitive resin composition according to an embodiment may further include a crosslinking agent. The crosslinking agent may be represented by one selected from chemical formulas 14-1 to 14-5.
[ chemical formula 14-1]
Figure BDA0002994901960000181
[ chemical formula 14-2]
Figure BDA0002994901960000182
[ chemical formula 14-3]
Figure BDA0002994901960000191
[ chemical formula 14-4]
Figure BDA0002994901960000192
[ chemical formulae 14 to 5]
Figure BDA0002994901960000193
In chemical formulas 14-1 to 14-5,
R11to R12Independently a hydrogen atom, or a substituted or unsubstituted C1 to C10 alkyl group,
R13to R22Independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C1 to C10 alkoxy group,
R23to R28Independently a hydrogen atom, or a substituted or unsubstituted C1 to C10 alkyl group,
L2is a substituted or unsubstituted C1 to C10 alkylene.
For example, R23To R28May independently be a C1 to C10 alkyl group substituted with an epoxy group. In this case, the reaction between the crosslinking agent and the polymer occurs more smoothly, and a crosslinked structure can be easily formed.
For example, R13To R22May independently be a C1 to C10 alkyl group substituted with a C1 to C5 alkoxy group. In this case, the reaction between the crosslinking agent and the polymer occurs more smoothly, and a crosslinked structure can be easily formed.
The crosslinking agent functions to prevent the taper angle from becoming small after the resin composition according to one embodiment is cured. Further, the resin composition further contains the above-mentioned thermal acid generator and a crosslinking agent, which reacts with the polymer and forms a crosslinked structure during baking of the organic film (resin film) after forming the pattern, and herein, the thermal acid generator promotes formation of the crosslinked structure of the crosslinking agent. Therefore, the resin composition can be cured at a relatively low temperature of 300 ℃ or less and more actively cross-linked, and thereby the heat resistance and chemical resistance of the baked organic film (resin film) are increased. Further, the organic film (resin film) generates less degassing after heating and baking, and thereby generation of dark spots in the organic film (resin film) is suppressed. In addition, the organic film may have a reduced shrinkage rate after curing.
The crosslinking agent may be included in an amount of 10 to 30 parts by weight, based on 100 parts by weight of the alkali soluble resin.
Dissolution control agent
The photosensitive resin composition according to an embodiment may further include a dissolution controlling agent having a structure other than the compound represented by chemical formula 1.
For example, the dissolution controlling agent may be represented by chemical formula 15.
[ chemical formula 15]
Figure BDA0002994901960000201
In the chemical formula 15, the first and second compounds,
R71to R80Independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C1 to C20 alkoxy group, or a substituted or unsubstituted C6 to C20 aryl group,
provided that R is71To R75And R76To R80At least one of which is a hydroxyl group, and
L1is a single bond, a substituted or unsubstituted C1 to C20 alkylene, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C6 to C20 arylene, or a combination thereof.
For example, the dissolution controlling agent may be represented by one of chemical formulas 15-1 to 15-7.
[ chemical formula 15-1]
Figure BDA0002994901960000202
(in chemical formula 15-1, R601Is a hydrogen atom or CH3And R is602To R606Independently is a hydrogen atom, OH or CH3)
[ chemical formula 15-2]
Figure BDA0002994901960000211
(in chemical formula 15-2, R607To R612Are identical or independently a hydrogen atom, OH or CH3)
[ chemical formula 15-3]
Figure BDA0002994901960000212
(in chemical formula 15-3, R613To R618Independently is a hydrogen atom, OH or CH3And R is619And R620Independently is a hydrogen atom or CH3。)
[ chemical formula 15-4]
Figure BDA0002994901960000213
[ chemical formulas 15-5]
Figure BDA0002994901960000214
(in chemical formula 15-5, R621To R626Independently a hydrogen atom or OH. )
[ chemical formulae 15-6]
Figure BDA0002994901960000215
[ chemical formulae 15 to 7]
Figure BDA0002994901960000221
The amount of the dissolution controlling agent may desirably be 1 part by weight to 30 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the amount of the dissolution controlling agent is included in this range, the dissolution rate and sensitivity of the exposed portion at the time of development with an aqueous alkali solution can be improved, and high-resolution pattern formation can be performed without a development residue (scum) during development.
Other additives
The positive photosensitive resin composition according to an embodiment may further include other additives.
The photosensitive resin composition may include the following additives: dibasic acids (such as malonic acid), alkanolamines (such as 3-amino-1, 2-propanediol), leveling agents, silane-based coupling agents, surfactants, epoxy compounds, free radical polymerization initiators, thermal latent acid generators, or combinations thereof, in order to prevent contamination of the film during coating, leveling improvement, or residue generation due to non-development. The amount of additive used can be controlled according to the desired properties.
For example, the silane-based coupling agent may have a reactive substituent (such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, an epoxy group, etc.) to improve close contact characteristics with the substrate.
Examples of the silane-based coupling agent may be trimethoxysilylbenzoic acid, gamma-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, gamma-isocyanatopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, etc., and may be used alone or in a mixture of two or more.
The silane-based coupling agent may be used in an amount of 0.01 to 10 parts by weight, based on 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is included within the above range, the close contact property, the storage property, and the like are improved.
For example, a surfactant is added to prevent strain of a film thickness or improve developability, and a fluorine-based surfactant and/or a silicone-based surfactant may be included.
Fluorine-based surfactantExamples of (A) may be commercial fluorine-based surfactants, such as, for example, those of MChemie Inc
Figure BDA0002994901960000222
And
Figure BDA0002994901960000223
dainippon Ink Kagaku Kogyo Co., Ltd MEGAFACE F
Figure BDA0002994901960000224
MEGAFACE F
Figure BDA0002994901960000225
MEGAFACE F
Figure BDA0002994901960000226
MEGAFACE F
Figure BDA0002994901960000227
And MEGAFACE F
Figure BDA0002994901960000228
FULORAD from Sumitomo 3M Co., Ltd
Figure BDA0002994901960000229
FULORAD
Figure BDA00029949019600002210
FULORAD
Figure BDA00029949019600002211
And FULORAD
Figure BDA0002994901960000231
SURFLON from Asahi Glass co
Figure BDA0002994901960000232
SURFLON
Figure BDA0002994901960000233
SURFLON
Figure BDA0002994901960000234
SURFLON
Figure BDA0002994901960000235
And SURFON
Figure BDA0002994901960000236
Toray silicon Co., Ltd
Figure BDA0002994901960000237
Figure BDA0002994901960000238
Figure BDA0002994901960000239
And
Figure BDA00029949019600002310
and the like.
The silicone based surfactants can be BYK-307, BYK-333, BYK-361N, BYK-051, BYK-052, BYK-053, BYK-067A, BYK-077, BYK-301, BYK-322, BYK-325, and the like, which are prepared by BYK Chem and are commercially available.
The surfactant may be included in an amount of 0.001 parts by weight to 5 parts by weight, based on 100 parts by weight of the photosensitive resin composition. When the surfactant is contained in this range, coating uniformity may be ensured, stains may not be generated, and wetting on an ITO substrate or a glass substrate may be improved.
The photosensitive resin composition may further include an epoxy compound or the like as an additive to improve the close contact force. The epoxy compound may be an epoxy novolac acryl carboxylate resin, an o-cresol novolac epoxy resin, a phenol novolac epoxy resin, a tetramethyl diphenyl epoxy resin, a bisphenol a epoxy resin, an alicyclic epoxy resin, or a combination thereof.
When an epoxy compound is further contained, a radical polymerization initiator (such as a peroxide initiator or an azodiyl initiator) may also be contained.
The epoxy compound may be included in an amount of 0.01 to 5 parts by weight, based on 100 parts by weight of the photosensitive resin composition. When the epoxy compound is contained in this range, storage property, close contact force, and other characteristics can be improved.
The photosensitive resin composition may further include a latent heat acid generator. Examples of latent thermal acid generators may be: arylsulfonic acids such as p-toluenesulfonic acid or benzenesulfonic acid; perfluoroalkylsulfonic acids such as trifluoromethanesulfonic acid or trifluorobutanesulfonic acid; alkyl sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, or butanesulfonic acid; or a combination thereof, but is not limited thereto.
The latent heat acid generator is a catalyst for dehydration reaction and cyclization reaction of a polybenzoxazole precursor (a polyamide containing a phenolic hydroxyl group), and thus the cyclization reaction can be smoothly performed even in the case where the curing temperature is lowered.
In addition, the photosensitive resin composition according to the embodiment may further include predetermined amounts of other additives, such as an antioxidant, a stabilizer, and the like, unless the performance is deteriorated.
Another embodiment provides a photosensitive resin film manufactured by exposing, developing and curing the aforementioned positive photosensitive resin composition.
Another embodiment provides an electronic device including a positive photosensitive resin film.
The electronic device may be a semiconductor device.
The method for producing the photosensitive resin film is as follows.
(1) Coating and film formation
The photosensitive resin composition is coated on a substrate (such as a glass substrate or an ITO substrate) subjected to a predetermined pretreatment to have a desired thickness using a spin coating or slit coating method, a roll coating method, a screen printing method, an applicator method, or the like, and then, the coated substrate is heated at a temperature range of 70 ℃ to 150 ℃ for 1 minute to 10 minutes to remove a solvent and form a film.
(2) Exposure method
After placing a mask having a predetermined shape, the obtained photosensitive resin film is irradiated with active rays of 200nm to 500nm to form a desired pattern. The irradiation is performed by using a light source such as a mercury lamp, a metal halide lamp, an argon laser, or the like having a low pressure, a high pressure, or an ultrahigh pressure. X-rays, electron beams, and the like may also be used as necessary.
The exposure dose differs depending on the type of each component of the composition, its combination ratio and dry film thickness, but is less than or equal to 500J/cm when a high-pressure mercury lamp is used2(according to 365nm sensor).
(3) Development
In the developing method, after the exposure step, the pattern is obtained by dissolving and removing the exposed portion using a developing solution to leave only the unexposed portion.
(4) Post-treatment Process
The image pattern obtained by the development in the above process is post-heated to obtain a pattern having improved heat resistance, light resistance, close contact property, crack resistance, chemical resistance, high strength, and storage stability. For example, after development, heating may be carried out in a convection oven at 250 ℃ for 1 hour.
Detailed description of the embodiments
Hereinafter, the present invention will be described in more detail with reference to examples. These examples, however, are not to be construed in any way as limiting the scope of the disclosure.
(examples)
(Synthesis of alkali-soluble resin)
In a four-necked flask equipped with a stirrer, a temperature controller, a nitrogen injector and a condenser, 11.0g of bis (3-amino-4-hydroxyphenyl) (phenyl) phosphine oxide was dissolved in 280g N-methyl-2-pyrrolidone (NMP) while passing nitrogen therethrough. When the solid was completely dissolved, 9.9g of pyridine was added to the solution, and another solution prepared by dissolving 13.3g of 4,4' -oxybenzoyl chloride in 142g of N-methyl-2-pyrrolidone (NMP) was slowly added in a dropwise manner over 30 minutes while the temperature was maintained at 0 ℃ to 5 ℃. After the addition, the obtained mixture was reacted at 0 to 5 ℃ for 1 hour, and then stirred for 1 hour by raising the temperature to room temperature, and then the reaction was completed. 1.6g of 5-norbornene-2, 3-dicarboxylic anhydride was added thereto, and then stirred at 70 ℃ for 24 hours to complete the reaction. The reaction mixture was placed in a solution of water/methanol 10/1 (volume ratio) to form a precipitate, and the precipitate was filtered and washed thoroughly with water, and then dried under vacuum at 80 ℃ for 24 hours or more to prepare a Polybenzoxazole (PBO) precursor having a weight average molecular weight of 11100 g/mol.
(preparation of photosensitive resin composition)
Examples 1 to 7 and comparative example 1
Based on the compositions provided in table 1, a polybenzoxazole precursor was added and dissolved in γ (γ) -butyrolactone (GBL), a photosensitive diazoquinone compound, a cresol-based phenol resin, compounds of chemical formulas 1A to 1G, a crosslinking agent, and a silane coupling agent were added thereto, and then stirred at room temperature for 1 hour, and then a leveling agent was further added thereto and dissolved therein, and then filtered with a 0.45 μm PE syringe filter to obtain each photosensitive resin composition.
[ Table 1]
(unit: g)
Figure BDA0002994901960000251
(A) Alkali soluble resin
(A-1) polybenzoxazole precursor
(A-2) cresol-based phenol resin (KCR-6100)
(B) Photosensitive diazoquinone compound (Compound A)
[ chemical formula A ]
Figure BDA0002994901960000261
(in the chemical formula A, Q1、Q2And Q3Two of the quilt
Figure BDA0002994901960000262
Substituted and the remaining one is a hydrogen atom. )
(C) Dissolution control agent
(C-1) Compound represented by chemical formula 1A (Sigma-Aldrich Corporation)
[ chemical formula 1A ]
Figure BDA0002994901960000263
(C-2) Compound represented by chemical formula 1B (Sigma-Aldrich Corporation)
[ chemical formula 1B ]
Figure BDA0002994901960000264
(C-3) Compound represented by chemical formula 1C (Sigma-Aldrich Corporation) [ chemical formula 1C ]
Figure BDA0002994901960000271
(C-4) Compound represented by chemical formula 1D (Sigma-Aldrich Corporation) [ chemical formula 1D ]
Figure BDA0002994901960000272
(C-5) Compound represented by chemical formula 1E (Sigma-Aldrich Corporation) [ chemical formula 1E ]
Figure BDA0002994901960000273
(C-6) Compound represented by chemical formula 1F (Sigma-Aldrich Corporation) [ chemical formula 1F ]
Figure BDA0002994901960000274
(C-7) Compound represented by chemical formula 1G (Sigma-Aldrich Corporation) [ chemical formula 1G ]
Figure BDA0002994901960000281
(D) Solvent(s)
Gamma (gamma) -butyrolactone (GBL)
Crosslinking agent
1,3,4, 6-tetrakis (methoxymethyl) glycoluril (TCI Inc., T2058)
Other additives
(1) Silane coupling agent (KBM-5732%)
(2) Flatting agent (BYK-378)
Evaluation of
The photosensitive resin compositions according to examples 1 to 7 and comparative example 1 were respectively coated on 8-inch wafers and heated on a hot plate at 120 ℃ for 4 minutes to form a 10 μm-thick film.
The film was exposed to light using an i-line stepper (NSR i11D) from nikon, japan. While changing the exposure dose by using a mask having a pattern of different size, 50/50 seconds (2 puddles) were developed in a 2.38% TMAH aqueous solution at room temperature to dissolve the exposed portion, and washed with pure water for 30 seconds to form a pattern. The film was cured at 280 ℃ for 60 minutes under nitrogen atmosphere.
Thickness measurement was performed using ST-5000(K-MAC) to confirm the film residue ratio (%). Using Hitachi S-9260CD-SEM, the optimum exposure dose in which a 7 μm hole pattern was precisely patterned was confirmed, and the sensitivity (7 μm hole Eop), the residual film rate, and the occurrence of scum are shown in 2.
Evaluation of scum appearance
O: scum appears
X: no scum appears
[ Table 2]
Figure BDA0002994901960000282
Figure BDA0002994901960000291
As shown in table 2, the positive photosensitive resin composition according to one embodiment includes a compound having a specific structure as a dissolution control agent, so that sensitivity and a film residue rate are greatly improved while generating no scum, as compared to a positive photosensitive resin composition that does not include a dissolution control agent of the structure.
While the invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not to be limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. The above embodiments are therefore to be understood as illustrative and not restrictive in any way.

Claims (12)

1. A positive photosensitive resin composition comprising
(A) An alkali-soluble resin;
(B) a photosensitive diazoquinone compound;
(C) a compound represented by chemical formula 1; and
(D) solvent:
[ chemical formula 1]
Figure FDA0002994901950000011
Wherein, in chemical formula 1,
R1is a hydrogen atom, or a substituted or unsubstituted C1 to C20 alkyl group,
R2and R3Independently is a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group, and
n is an integer of 0 or 1.
2. The positive photosensitive resin composition according to claim 1, wherein chemical formula 1 is represented by chemical formula 1-1 or chemical formula 1-2:
[ chemical formula 1-1]
Figure FDA0002994901950000012
[ chemical formulas 1-2]
Figure FDA0002994901950000021
Wherein, in chemical formula 1-1 and chemical formula 1-2,
R4is a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group,
R5is unsubstituted C1 to C20 alkyl,
R6is a substituted or unsubstituted C1 to C20 alkyl group, and
n is an integer of 0 or 1.
3. The positive photosensitive resin composition according to claim 2, wherein chemical formula 1-1 is represented by one of chemical formula 1-1-1 to chemical formula 1-1-3:
[ chemical formula 1-1-1]
Figure FDA0002994901950000022
[ chemical formulas 1-1-2]
Figure FDA0002994901950000023
[ chemical formulas 1-1-3]
Figure FDA0002994901950000031
Wherein, in chemical formulas 1-1-1 to 1-1-3,
R7is a substituted or unsubstituted C1 to C20 alkoxy group,
R8is a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group, and
R9is-CRaRbRc(wherein, Ra、RbAnd RcIndependently is a substituted or unsubstituted C1 to C10 alkyl group, provided that Ra、RbAnd RcAt least one of which is different from the other two).
4. The positive photosensitive resin composition according to claim 2, wherein chemical formula 1-2 is represented by chemical formula 1-2-1 or chemical formula 1-2-2:
[ chemical formula 1-2-1]
Figure FDA0002994901950000032
[ chemical formula 1-2-2]
Figure FDA0002994901950000033
Wherein, in chemical formula 1-2-1 and chemical formula 1-2-2,
R5is unsubstituted C1 to C20 alkyl, and
R10is a substituted or unsubstituted C1 to C20 alkyl group.
5. The positive photosensitive resin composition according to claim 1, wherein the compound represented by chemical formula 1 is represented by one of chemical formula 1A to chemical formula 1F:
[ chemical formula 1A ]
Figure FDA0002994901950000041
[ chemical formula 1B ]
Figure FDA0002994901950000042
[ chemical formula 1C ]
Figure FDA0002994901950000043
[ chemical formula 1D ]
Figure FDA0002994901950000044
[ chemical formula 1E ]
Figure FDA0002994901950000051
[ chemical formula 1F ]
Figure FDA0002994901950000052
6. The positive photosensitive resin composition according to claim 1, wherein the compound represented by chemical formula 1 is included in an amount of 0.5 to 40 parts by weight based on 100 parts by weight of the alkali soluble resin.
7. The positive photosensitive resin composition according to claim 1, wherein the alkali soluble resin comprises a polybenzoxazole precursor, a polyimide precursor, a phenolic resin, or a combination thereof.
8. The positive photosensitive resin composition according to claim 1, wherein the positive photosensitive resin composition further comprises a crosslinking agent.
9. The positive photosensitive resin composition according to claim 1,
the positive photosensitive resin composition comprises
Based on 100 parts by weight of the alkali soluble resin,
the photosensitive diazoquinone compound is contained in an amount of 5 parts by weight to 50 parts by weight, and
the compound represented by chemical formula 1 is contained in an amount of 0.5 to 40 parts by weight, and
the solvent is included in an amount of 100 parts by weight to 500 parts by weight.
10. The positive photosensitive resin composition according to claim 1, further comprising the following additives: a dibasic acid, an alkanolamine, a leveling agent, a silane-based coupling agent, a surfactant, an epoxy compound, a free radical polymerization initiator, a thermal latent acid generator, or a combination thereof.
11. A photosensitive resin film produced using the positive photosensitive resin composition according to any one of claim 1 to claim 10.
12. An electronic device comprising the photosensitive resin film according to claim 11.
CN201980063779.2A 2018-09-28 2019-07-23 Positive photosensitive resin composition, photosensitive resin film using the same, and electronic device Pending CN112771447A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR1020180116383A KR102319968B1 (en) 2018-09-28 2018-09-28 Positive photosensitive resin composition, photosensitive resin layer and electronic device using the same
KR10-2018-0116383 2018-09-28
PCT/KR2019/009112 WO2020067638A1 (en) 2018-09-28 2019-07-23 Positive photosensitive resin composition, photosensitive resin film using same, and electronic device

Publications (1)

Publication Number Publication Date
CN112771447A true CN112771447A (en) 2021-05-07

Family

ID=69952204

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201980063779.2A Pending CN112771447A (en) 2018-09-28 2019-07-23 Positive photosensitive resin composition, photosensitive resin film using the same, and electronic device

Country Status (3)

Country Link
KR (1) KR102319968B1 (en)
CN (1) CN112771447A (en)
WO (1) WO2020067638A1 (en)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5875519B2 (en) * 2010-09-03 2016-03-02 昭和電工株式会社 Photosensitive resin and method for producing photosensitive resin composition containing the photosensitive resin
KR101400181B1 (en) * 2010-12-30 2014-06-27 삼성디스플레이 주식회사 Positive photosensitive resin composition, photosensitive resin layer prepared by using the same, and display device including the photosensitive resin layer
KR20140057957A (en) * 2012-11-05 2014-05-14 도레이케미칼 주식회사 Positive polyamide varnish and polyimide film
KR20140057961A (en) * 2012-11-05 2014-05-14 도레이케미칼 주식회사 Positive polyamide varnish and polyimide film
KR101667787B1 (en) * 2013-08-13 2016-10-19 제일모직 주식회사 Positive photosensitive resin composition, and photosensitive resin film and display device prepared by using the same
JP6233271B2 (en) * 2013-12-27 2017-11-22 Jsr株式会社 Photosensitive resin composition and method for producing resist pattern
KR20160104380A (en) * 2015-02-26 2016-09-05 삼성에스디아이 주식회사 Positive photosensitive resin composition, photosensitive resin film and display device using the same
KR102044944B1 (en) * 2016-11-16 2019-11-14 삼성에스디아이 주식회사 Photosensitive resin composition, photosensitive resin layer using the same and display device

Also Published As

Publication number Publication date
KR102319968B1 (en) 2021-10-29
KR20200036573A (en) 2020-04-07
WO2020067638A1 (en) 2020-04-02

Similar Documents

Publication Publication Date Title
TWI548945B (en) Positive photosensitive resin composition, photosensitive resin film and display device using the same
KR102319968B1 (en) Positive photosensitive resin composition, photosensitive resin layer and electronic device using the same
TWI709820B (en) Positive photosensitive resin composition, photosensitive resin layer and electronic device
KR102044944B1 (en) Photosensitive resin composition, photosensitive resin layer using the same and display device
TWI738071B (en) Photosensitive resin composition, photosensitive resin layer and electronic device
CN110874015B (en) Photosensitive resin composition, photosensitive resin layer using same, and electronic device
KR102149967B1 (en) Photosensitive resin composition and photosensitive resin layer using the same
CN110501874B (en) Photosensitive resin composition, photosensitive resin layer, and electronic device
CN110501877B (en) Photosensitive resin composition, photosensitive resin layer using same, and electronic device
TWI696038B (en) Photosensitive resin composition, photosensitive resin layer using the same and electronic device
KR102302049B1 (en) Photosensitive resin composition, photosensitive resin layer and electronic device using the same
KR102252996B1 (en) Photosensitive resin composition, photosensitive resin layer using the same and electronic device
KR102302050B1 (en) Photosensitive resin composition, photosensitive resin layer and electronic device using the same
KR101720717B1 (en) Positive photosensitive resin composition, photosensitive resin film, and display device using the same
KR20230174962A (en) Photosensitive resin composition, photosensitive resin layer using the same, micro lens, cmos image sensor and device comprising the same
JP2015049457A (en) Photosensitive resin material, electronic device, and production method of photosensitive resin material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination