CN117866200A - Polybenzoxazole precursor, process for producing the same, and photosensitive resin composition - Google Patents

Polybenzoxazole precursor, process for producing the same, and photosensitive resin composition Download PDF

Info

Publication number
CN117866200A
CN117866200A CN202311742221.1A CN202311742221A CN117866200A CN 117866200 A CN117866200 A CN 117866200A CN 202311742221 A CN202311742221 A CN 202311742221A CN 117866200 A CN117866200 A CN 117866200A
Authority
CN
China
Prior art keywords
formula
polybenzoxazole precursor
group
acid
dicarboxylic acid
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
CN202311742221.1A
Other languages
Chinese (zh)
Inventor
路庆华
韩晓宇
秦蔚临
王博
单锋
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.)
Mingshi New Materials Co ltd
Shanghai Mingshihua New Materials Co ltd
Shanghai Jiaotong University
Original Assignee
Mingshi New Materials Co ltd
Shanghai Mingshihua New Materials Co ltd
Shanghai Jiaotong University
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 Mingshi New Materials Co ltd, Shanghai Mingshihua New Materials Co ltd, Shanghai Jiaotong University filed Critical Mingshi New Materials Co ltd
Priority to CN202311742221.1A priority Critical patent/CN117866200A/en
Publication of CN117866200A publication Critical patent/CN117866200A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/22—Polybenzoxazoles
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

Disclosed herein are a benzoxazole precursor, a method of preparing the same, and a photosensitive resin composition, wherein the benzoxazole precursor is formed by reacting a diamine monomer and a dicarboxylic acid monomer; wherein the diamine monomer comprises a diamine compound shown in a formula (1) and/or a formula (2), and the dicarboxylic acid monomer has a structure shown in a formula (3). The polybenzoxazole precursor can effectively reduce the heat curing temperature, and has good mechanical property, thermal property, photoetching property and chemical corrosion resistance.

Description

Polybenzoxazole precursor, process for producing the same, and photosensitive resin composition
Technical Field
The application relates to the technical field of photosensitive polymers, in particular to a polybenzoxazole precursor, a preparation method of the polybenzoxazole precursor and a photosensitive resin composition.
Background
Polyimide (PI) and Polybenzoxazole (PBO) have been widely used as stress buffer coatings and covercoat films for wafer level chip scale packages with copper redistribution layers (RDLs) to improve the reliability of semiconductor devices, provide precise bump height uniformity and bump shape control for the most complex wafer layout, while maintaining low deposition internal stress, due to their excellent thermal, mechanical and electrical properties, as well as good chemical resistance. Advanced packaging technologies, such as multi-layer RDL, 3D stacking and Heterogeneous Integration (HI), enable a variety of chips and chiplets with different functions, capabilities, sizes and sources to work cooperatively in a system, attached to substrates ranging from silicon and fan-out to organic and glass.
Photosensitive Polybenzoxazole (PBO) has photosensitive characteristics, patterns are developed through coating, exposure and development, and the photosensitive Polybenzoxazole (PBO) is used as an insulating protective layer to realize large-scale application in the field of microelectronic packaging. The curing temperature of PBO is generally above 300 ℃, but in the fields of fan-out wafer level package (FOWLP), fan-out flat panel level package (FOPLP) and the like, during the high temperature curing process, the wafer may warp, and the solder joint of the low-melting solder of the plastic package circuit may crack, fall off, recrystallize and the like, so that the performance of the plastic package device is seriously damaged, and considering the fan-shaped external stress, the transition to the full Cu interconnection is required, so that the high temperature curing temperature of PBO is limited to 250 ℃, and therefore, the PBO must be cured more quickly at a lower temperature, and meanwhile, the adhesion, mechanical property, thermal property and the like of the PBO with a copper substrate should not be lost.
Compared with the high-temperature curing type PBO, the low-temperature curing type PBO solves the problems of wafer warpage and the like possibly caused by high-temperature curing, and simultaneously can keep the mechanical property, the thermal property and the like unaffected. Therefore, in recent years, low-temperature curing type PBO has been the focus of research.
Disclosure of Invention
The purpose of the application is to provide a polybenzoxazole precursor which can effectively reduce the heat curing temperature and has good mechanical property, thermal property, photoetching property and chemical corrosion resistance.
In order to achieve the above object, the technical solution of the present application provides a polybenzoxazole precursor formed by the reaction of a diamine monomer and a dicarboxylic acid monomer; wherein the diamine monomer comprises a diamine compound represented by formula (1) and/or formula (2):
the dicarboxylic acid monomer has a structure represented by formula (3):
in formula (3), X is a divalent organic group that is an aliphatic group or an aromatic group; z is selected from hydroxyl or halogen groups.
In some embodiments of the present application, the monovalent organic group is selected from the group consisting of C1-C12 alkyl, C1-C12 alkoxy, C6-C10 aromatic, C6-C10 phenoxy, C6-C10 benzyl, and C6-C10 benzyloxy; at R 1 ～R 5 In and R 11 ～R 51 Wherein 0 to 3 groups are independently selected from the monovalent organic groups, and the remaining groups are hydrogen; preferably, at R 1 ～R 5 In and R 11 ～R 51 Wherein each of the radicals is independently selected from the monovalent organic groups, the remaining radicals are hydrogen, or R 1 ～R 5 R is R 11 ～R 51 Are all hydrogen.
In some embodiments of the present application, X is a C6-C48 aromatic group; excellent (excellent)Optionally, X is an aromatic group of C6-C24; further preferably, the X is Wherein A is selected from the group consisting of single bond, alkylene, -O-, -and- >-S-、/>-C(CF 3 ) 2 -and-C (CH) 3 ) 2 -, represents a linker to the carbonyl group in formula (3).
In some embodiments of the present application, the dicarboxylic acid monomer is selected from at least one of an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, a dihalide or a dicarboxylic acid ester of the aromatic dicarboxylic acid, a dihalide or a dicarboxylic acid ester of the aliphatic dicarboxylic acid; preferably, the method comprises the steps of, the aromatic dicarboxylic acid is selected from isophthalic acid, terephthalic acid, 5-tert-butyl isophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2, 6-naphthalene dicarboxylic acid, 4' -dicarboxybiphenyl 4,4' -dicarboxydiphenyl ether, 4' -dicarboxydiphenyl silane, bis (4-carboxyphenyl) sulfone at least one of 2, 2-bis (p-carboxyphenyl) propane and 2, 2-bis (4-carboxyphenyl) -1, 3-hexafluoropropane; preferably, the aliphatic dicarboxylic acid is at least one selected from oxalic acid, malonic acid, succinic acid, 1, 2-cyclobutanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, and 1, 3-cyclopentanedicarboxylic acid.
In some embodiments of the present application, the diamine monomer further comprises a diamine compound of formula (4):
in the formula (4), Y is a tetravalent organic group having at least two or more hydroxyl groups, the tetravalent organic group being an aliphatic group or an aromatic group; preferably, the tetravalent organic group is an aromatic group.
In some embodiments of the present application, the Y is selected from the following tetravalent organic groups:
wherein one of 1 and 2 represents a linking moiety with an amino group in formula (4), and the other represents a linking moiety with a hydroxyl group in Y in formula (4).
In some embodiments of the present application, the polybenzoxazole precursor has a structural formula as shown in formula (I) or formula (II):
in the formula (I) and the formula (II), X isY is->
n and n1 are 1 to 100, m and m1 are 0 to 100; preferably, n and n1 are 1 to 40, and m1 are 15 to 40.
The application also provides a preparation method of the polybenzoxazole precursor, which comprises the following steps: s1: dissolving diamine monomer in a first solvent to obtain diamine monomer solution, wherein the mole percentage of diamine compounds shown in the formula (1) and/or the formula (2) in the diamine monomer is 10% -100%; s2: and adding a dicarboxylic acid monomer shown in the formula (3) into the diamine monomer solution, and performing polymerization reaction to obtain a polybenzoxazole precursor solution.
In some embodiments of the present application, the first solvent is selected from at least one of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, tetrahydrofuran, 1, 3-dimethyl-2-imidazolidinone, γ -butyrolactone, ethyl acetate, butyl acetate, N-propyl acetate, methyl lactate, ethylene lactate, propyl lactate, butyl lactate, toluene, xylene, mesitylene, diacetone alcohol, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, methylpropyl ketone, tetrahydrofuran, tetrahydropyran, dioxane, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate;
And/or, step S2 satisfies one of the following conditions: 1) Adding dicarboxylic acid monomers shown in the formula (3) under the ice bath condition of 0-10 ℃, wherein the polymerization reaction temperature is 0-35 ℃ and the polymerization reaction time is 2-10 hours; 2) The molar ratio of the diamine monomer to the dicarboxylic acid monomer shown in the formula (3) is 1 (0.5-1);
and/or, the preparation method further comprises the step S3: adding a blocking agent into the polybenzoxazole precursor solution to perform a blocking reaction to obtain a blocked polybenzoxazole precursor solution, wherein the molar ratio of the blocking agent to the diamine monomer is (0.02-0.2): 1, the temperature of the blocking reaction is 10-35 ℃ and the time is 1-4 hours; preferably, the end-capping agent is selected from at least one of phthalic anhydride, maleic anhydride, succinic anhydride, 2, 3-pyrazinedicarboxylic anhydride, tetrafluorophthalic anhydride, 2, 3-naphthalenedicarboxylic anhydride, hexahydrophthalic anhydride, norbornenedicarboxylic anhydride, tetrahydrophthalic anhydride, 4-phenylalkynylphthalic anhydride, bicyclo [2.2.2] oct-5-ene-2, 3-dicarboxylic anhydride, phenylsuccinic anhydride, 2' -biphenyldicarboxylic anhydride;
and/or, the preparation method further comprises the step S4: dripping the polybenzoxazole precursor solution or the end-capped polybenzoxazole precursor solution into deionized water, and washing and drying the precipitate to obtain the dried polybenzoxazole precursor.
The application also provides a photosensitive resin composition which comprises the following components in parts by weight: 100 parts of polybenzoxazole precursor, 5 to 40 parts of photosensitizer and 30 to 10000 parts of second solvent; preferably, the photosensitizer comprises at least one of photoacid generator, photobase generator, crosslinking agent, thermal acid generator, sensitizer, thickener, surfactant, leveling agent, and fine particles; preferably, the second solvent includes at least one of N, N '-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N' -dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ -butyrolactone, α -acetyl- γ -butyrolactone, tetramethylurea, 1, 3-dimethyl-2-imidazolidinone, N-cyclohexyl-2-pyrrolidone, dimethylsulfoxide, hexamethylphosphoramide, pyridine, γ -butyrolactone, and diethylene glycol monomethyl ether.
According to the preparation method, the diamine monomer containing the cyclohexyl is introduced, so that the prepared polybenzoxazole precursor contains six-membered ring side groups, the close arrangement of the polybenzoxazole precursor molecular chains is limited by larger steric hindrance, and the energy required by the polybenzoxazole precursor in the heating and ring-closing process is reduced, so that the polybenzoxazole precursor can realize ring-closing solidification at a lower solidification temperature, the cyclization rate is improved, the polybenzoxazole precursor has better mechanical property, thermal property, photoetching property and chemical corrosion resistance, and the problem that the devices with lower heat resistance are possibly damaged in the fields of fan-out wafer level packaging, fan-out flat plate level packaging and the like in the high-temperature thermal solidification process is effectively avoided.
The photosensitive resin composition containing the polybenzoxazole precursor can be used as a positive photoresist developed by alkaline water, can form high-resolution patterns in photoetching, has excellent mechanical and thermal properties, and can improve the related performance of a black matrix when applied to the black matrix.
The preparation method of the polybenzoxazole precursor has the advantages of convenient and easily obtained raw materials, simple preparation steps and process conditions, easy control and convenient industrialized popularization and application.
Drawings
The following figures describe in detail exemplary embodiments disclosed in the present application. Wherein like reference numerals refer to like structure throughout the several views of the drawings. Those of ordinary skill in the art will understand that these embodiments are non-limiting, exemplary embodiments, and that the drawings are for illustration and description purposes only and are not intended to limit the scope of the present application, other embodiments may equally well accomplish the intent of the invention in this application. It should be understood that the drawings are not to scale. Wherein:
FIG. 1 is a structural formula of a polybenzoxazole precursor according to embodiments of the application;
FIG. 2 is another structural formula of a polybenzoxazole precursor according to embodiments of the application;
FIG. 3 is a FT-IR chart of a polybenzoxazole membrane prepared in example 7 of this application;
FIG. 4 is a graph showing a photolithography performance test of the photosensitive resin composition prepared in example 1 of the present application;
FIG. 5 is a graph showing the photolithography performance test of the photosensitive resin composition prepared in example 2 of the present application;
fig. 6 is a 3D view of the film surface after soaking in N-methyl pyrrolidone using the cured film of example 16 of the present application.
Detailed Description
The following description provides specific applications and requirements to enable any person skilled in the art to make and use the teachings of the present application. Various modifications to the disclosed embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the application. Thus, the present application is not limited to the embodiments shown, but is to be accorded the widest scope consistent with the claims.
Based on the problem that the fields such as fan-out wafer level packaging and fan-out flat plate level packaging possibly damage devices with lower heat resistance in the high-temperature heat curing process, the application improves the polybenzoxazole, introduces the six-membered ring side group into a molecular chain of a polybenzoxazole precursor, thereby reducing the heat curing temperature of the polybenzoxazole precursor and keeping other performances to meet the requirements.
Specifically, embodiments herein provide a polybenzoxazole precursor formed by the reaction of a diamine monomer and a dicarboxylic acid monomer. The diamine monomer comprises a diamine compound shown in a formula (1) and/or a formula (2):
in the formula (1) and the formula (2), R 1 ～R 5 、R 11 ～R 51 Independently selected from hydrogen or monovalent organic groups.
In some preferred embodiments, the monovalent organic group is selected from the group consisting of C1-C12 alkyl, C1-C12 alkoxy, C6-C10 aromatic, C6-C10 phenoxy, C6-C10 benzyl, and C6-C10 benzyloxy. The C1-C12 alkyl group is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl or the like; the C1-C12 alkoxy group is, for example, methoxy, ethoxy, propoxy, butoxy, pentyloxy or the like; examples of the aromatic group having 6 to 10 carbon atoms include phenyl, tolyl, methylphenyl, dimethylphenyl, ethylphenyl, diethylphenyl, propylphenyl, butylphenyl, fluorophenyl, pentafluorophenyl, chlorophenyl, bromophenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, diethoxyphenyl, methoxybenzyl, dimethoxybenzyl, ethoxybenzyl, diethoxybenzyl, aminophenyl, aminobenzyl, nitrophenyl, nitrobenzyl, cyanophenyl, cyanobenzyl, phenethyl, phenylpropyl, phenylamino, diphenylamino, biphenyl, naphthyl and the like; the phenoxy group having 6 to 10 carbon atoms is, for example, methylphenoxy, ethylphenoxy, propylphenoxy, dimethylphenoxy, diethylphenoxy, methoxyphenoxy, ethoxyphenoxy, dimethoxyphenoxy or the like; the C6-C10 benzyl group is, for example, benzyl, methylbenzyl, ethylbenzyl, propylbenzyl, dimethylbenzyl, methoxybenzyl, ethoxybenzyl, methoxybenzyl or the like; the C6-C10 benzyloxy group is, for example, methylbenzyloxy group, benzyloxy group, pentylbenzyloxy group, ethylbenzyloxy group, propylbenzyloxy group, dimethylbenzyloxy group, methoxybenzyloxy group, ethoxybenzyloxy group or the like.
In order to further reduce the curing temperature of the photosensitive resin composition, improve the heat resistance and chemical corrosion resistance of the cured film, etc., R is 1 ～R 5 In and R 11 ～R 51 Wherein 0 to 3 groups are independently selected from the monovalent organic groups, and the remainder are hydrogen. Preferably, at R 1 ～R 5 In and R 11 ～R 51 Wherein one of the radicals is independently selected from the monovalent organic radicals, the remaining radicals are each hydrogen, i.e. in R 1 ～R 5 One of the groups is selected from the monovalent organic groups, the remaining groups are hydrogen, while at R 11 ～R 51 One group is selected from the monovalent organic groups, and the rest groups are all hydrogen; alternatively, R 1 ～R 5 R is R 11 ～R 51 Are all hydrogen.
The dicarboxylic acid monomer has a structure represented by formula (3):
in the formula (3), X is a divalent organic group which is an aliphatic group or an aromatic group, preferably a C6 to C48 aromatic group, and more preferably a C6 to C24 aromatic group. More preferably, X isWherein A is selected from the group consisting of single bond, alkylene, -O-, -and->-S-、/>-C(CF 3 ) 2 -and-C (CH) 3 ) 2 -, represents a carbonyl group of formula (2)>Is provided.
In order to further improve the developability of the photosensitive resin composition and the mechanical properties of the cured film, A is-O-, in which X is
In formula (3), Z is selected from hydroxyl or halogen groups. To further increase the yield, Z is preferably a halogen group.
In some embodiments, the dicarboxylic acid monomer is selected from at least one of an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, a dihalide of the aromatic dicarboxylic acid, a dicarboxylic acid ester of the aromatic dicarboxylic acid, a dihalide of the aliphatic dicarboxylic acid, and a dicarboxylic acid ester of the aliphatic dicarboxylic acid. Preferably, the method comprises the steps of, the aromatic dicarboxylic acid is selected from isophthalic acid, terephthalic acid, 5-tert-butyl isophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2, 6-naphthalene dicarboxylic acid, 4' -dicarboxybiphenyl 4,4' -dicarboxydiphenyl ether, 4' -dicarboxydiphenyl silane, bis (4-carboxyphenyl) sulfone at least one of 2, 2-bis (p-carboxyphenyl) propane and 2, 2-bis (4-carboxyphenyl) -1, 3-hexafluoropropane. Preferably, the aliphatic dicarboxylic acid is at least one selected from oxalic acid, malonic acid, succinic acid, 1, 2-cyclobutanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid and 1, 3-cyclopentanedicarboxylic acid.
In order to further improve the developability of the photosensitive resin composition and the mechanical properties of the cured film, the dicarboxylic acid-based monomer is preferably 4,4' -dicarboxydiphenyl ether (i.e., 4' -diphenylether dicarboxylic acid) and dihalides thereof (e.g., 4' -diacid chloride diphenyl ether).
In some embodiments, the diamine monomer further comprises a diamine compound of formula (4):in formula (4), Y is a tetravalent organic group having at least two or more hydroxyl groups. The tetravalent organic group may be an aliphatic group or an aromatic group, preferably an aromatic group. The hydroxyl group in YThe positional relationship of the group to the amino group in formula (4) is preferably ortho. The number of carbon atoms of Y is preferably 6 to 48, more preferably 6 to 24.
In some preferred embodiments, the Y is selected from the following tetravalent organic groups:
in the above tetravalent organic group, one of 1 and 2 represents an amino group (-NH) in formula (4) 2 ) The other represents a connection to a hydroxyl group.
In order to further improve the solubility and photosensitivity of the polybenzoxazole precursor in an alkali developer, Y isThe diamine compound shown in the formula (4) is 3,3 '-diamino-4, 4' -dihydroxydiphenyl sulfone, and the structural formula is as follows:
in some preferred embodiments, Y isThe diamine compound represented by the formula (4) is 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, which has the following structural formula:
in some embodiments, the polybenzoxazole precursor has a structural formula of formula I as shown in fig. 1 or formula II as shown in fig. 2. In the formula (I) and the formula (II), X is Y isn and n1 are 1 to 100, and m1 are 0 to 100. More preferably, n and n1 are 1 to 40, and m1 are 15 to 40.
In order to further improve the solubility of the photosensitive resin composition in an alkali developer, the number average molecular weight (Mn) of the polybenzoxazole precursor is preferably 2000 to 40000, more preferably 3000 to 20000; preferably the polybenzoxazole precursor has a weight average molecular weight (Mw) of 4000 to 80000, more preferably 6000 to 40000. The Mw/Mn of the polybenzoxazole precursor is preferably 1 to 5, more preferably 1 to 3. In the examples herein, the number average molecular weight and the weight average molecular weight are both determined using Gel Permeation Chromatography (GPC).
In order to further improve the lithographic performance and low-temperature curing performance of the polybenzoxazole precursor, n/(m+n) ×100% is not less than 0.1%, and n 1/(m1+n1) ×100% is not less than 0.1% in the formula (I) and the formula (II). More preferably, n/(m+n). Times.100%. Gtoreq.0.5%, and n 1/(m1+n1). Times.100%. Gtoreq.5%. Wherein, n/(m+n). Times.100% also represents the length ratio of the polymer chain segment formed by polymerizing the diamine compound shown in formula (1) and the dicarboxylic acid monomer in the total molecular chain of the polybenzoxazole precursor, and represents the molar percentage content of the diamine compound shown in formula (1) in the diamine monomer. In the same way, n 1/(m1+n1) ×100% also represents the length ratio of the polymer segment formed by polymerizing the diamine compound represented by formula (2) and the dicarboxylic acid monomer in the total molecular chain of the polybenzoxazole precursor, and represents the molar percentage of the diamine compound represented by formula (2) in the diamine monomer.
In some embodiments, the diamine monomer may include at least one of the following diamine compounds in addition to the diamine compound(s) represented by formula (1) and/or formula (2) and the diamine compound(s) represented by formula (4): 4,4' -bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl ] ketone, bis [4- (3-aminophenoxy) phenyl ] sulfide bis [4- (3-aminophenoxy) phenyl ] sulfone, 2-bis [4- (3-aminophenoxy) phenyl ] propane, 2-bis [4- (3-aminophenoxy) phenyl ] -1, 3-hexafluoropropane m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 3 ' -diaminodiphenyl ether, 3, 4' -diaminodiphenyl ether, 4' -diaminodiphenyl ether, 3 ' -diaminodiphenyl sulfide, 3 ' -diaminodiphenyl sulfoxide, and 3, 4' -diaminodiphenyl sulfoxide, 4' -diaminodiphenyl sulfoxide, 3 ' -diaminodiphenyl sulfone, 3, 4' -diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfone 3,3 ' -diaminobenzophenone, 3, 4' -diaminobenzophenone, 4' -diaminobenzophenone, 3 ' -diaminodiphenylmethane 3, 4' -diaminodiphenylmethane, 4' -diaminodiphenylmethane, bis [4- (4-aminophenoxy) phenyl ] methane, 1-bis [4- (4-aminophenoxy) phenyl ] ethane, 1, 2-bis [4- (4-aminophenoxy) phenyl ] ethane, 1-bis [4- (4-aminophenoxy) phenyl ] propane, 1, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 1, 3-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 1-bis [4- (4-aminophenoxy) phenyl ] butane, 1, 3-bis [4- (4-aminophenoxy) phenyl ] butane, 1, 4-bis [4- (4-aminophenoxy) phenyl ] butane, 2-bis [4- (4-aminophenoxy) phenyl ] butane, 2, 3-bis [4- (4-aminophenoxy) phenyl ] butane 2- [4- (4-aminophenoxy) phenyl ] -2- [4- (4-aminophenoxy) -3-methylphenyl ] propane, 2-bis [4- (4-aminophenoxy) -3-methylphenyl ] propane, 2- [4- (4-aminophenoxy) phenyl ] -2- [4- (4-aminophenoxy) -3, 5-dimethylphenyl ] propane 2, 2-bis [4- (4-aminophenoxy) -3, 5-dimethylphenyl ] propane, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane, 1, 4-bis (3-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl ] ketone, bis [4- (4-aminophenoxy) phenyl ] sulfide, bis [4- (4-aminophenoxy) phenyl ] sulfoxide, bis [4- (4-aminophenoxy) phenyl ] sulfone, bis [4- (3-aminophenoxy) phenyl ] ether, bis [4- (4-aminophenoxy) phenyl ] ether, 1, 3-bis [4- (4-aminophenoxy) benzoyl ] benzene, 1, 3-bis [4- (3-aminophenoxy) benzoyl ] benzene, 1, 4-bis [4- (3-aminophenoxy) benzoyl ] benzene, 4' -bis [ (3-aminophenoxy) benzoyl ] benzene, 1-bis [4- (3-aminophenoxy) phenyl ] propane, 1, 3-bis [4- (3-aminophenoxy) phenyl ] propane, 3, 4' -bis [4- (4-aminophenoxy) phenyl ] ether, bis [2, 3-aminophenoxy ] propane, 1, 3-bis [ 3-aminophenoxy ] methane, 1, 3-bis [4- (3-aminophenoxy) phenyl ] propane, 1, 2-bis [4- (3-aminophenoxy) phenyl ] ethane, bis [4- (3-aminophenoxy) phenyl ] sulfoxide, 4 '-bis [3- (4-aminophenoxy) benzoyl ] diphenyl ether, 4' -bis [3- (3-aminophenoxy) benzoyl ] diphenyl ether, 4 '-bis [4- (4-amino-alpha, alpha-dimethylbenzyl) phenoxy ] benzophenone, 4' -bis [4- (4-amino-alpha, alpha-dimethylbenzyl) phenoxy ] diphenyl sulfone, bis [4- {4- (4-aminophenoxy) phenoxy } phenyl ] sulfone, 1, 4-bis [4- (4-aminophenoxy) phenoxy-alpha, alpha-dimethylbenzyl ] benzene, 1, 3-bis [4- (4-amino-6-trifluoromethylphenoxy) -alpha, alpha-dimethylbenzyl ] benzene, 1, 3-bis [4- (4-amino-alpha, alpha-dimethylbenzyl) -benzene, alpha, 1, 4-bis [4- (4-aminophenoxy) -alpha, 6-dimethylbenzyl ] benzene, alpha, 1, 3-bis [4- (4-aminophenoxy) -alpha, 6-dimethylbenzyl) benzene, alpha-dimethylbenzyl ] benzene, 3 '-diamino-4, 4' -diphenoxybenzophenone, 4 '-diamino-5, 5' -diphenoxybenzophenone, 3,4 '-diamino-4, 5' -diphenoxybenzophenone, 3 '-diamino-4-phenoxybenzophenone, and 4,4' -diamino-5-phenoxybenzophenone, 3,4 '-diamino-4-phenoxybenzophenone, 3, 4' -diamino-5 '-phenoxybenzophenone, 3' -diamino-4, 4 '-diphenoxybenzophenone, 4' -diamino-5, 5 '-diphenoxybenzophenone, 3, 4' -diamino-4, 5 '-biphenoxybenzophenone, 3' -diamino-4-biphenoxybenzophenone, 4 '-diamino-5-biphenoxybenzophenone, 3, 4' -diamino-4-biphenoxybenzophenone, 3,4 '-diamino-5' -biphenoxybenzophenone, 1, 3-bis (3-amino-4-phenoxybenzoyl) benzene, 1, 4-bis (3-amino-4-phenoxybenzoyl) benzene, 1, 3-bis (4-amino-5-phenoxybenzoyl) benzene, 1, 4-bis (4-amino-5-phenoxybenzoyl) benzene, 1, 3-bis (3-amino-4-biphenoxybenzoyl) benzene, and an aromatic diamine in which all or part of hydrogen atoms on an aromatic ring in the aromatic diamine are replaced with a halogen atom, an alkyl group or an alkoxy group having 1 to 3 carbon atoms, a cyano group, or a haloalkyl group or an alkoxy group having 1 to 3 carbon atoms, in which all or part of hydrogen atoms of the alkyl group or the alkoxy group are replaced with a halogen atom, and the like, and wherein 1, 4-bis (3-amino-4-diphenoxybenzoyl) benzene, 1, 3-bis (4-amino-5-diphenoxybenzoyl) benzene, 2, 6-bis [4- (4-amino-. Alpha.,. Alpha. -dimethylbenzyl) phenoxy ] benzonitrile, and the like; aliphatic diamines such as 4,4' -methylenebis (cyclohexylamine), isophorone diamine, trans-1, 4-diaminocyclohexane, cis-1, 4-diaminocyclohexane, 1, 4-cyclohexanediamine, 2, 5-bis (aminomethyl) bicyclo [2, 1] heptane, 2, 6-bis (aminomethyl) bicyclo [2, 1] heptane, 3, 8-bis (aminomethyl) tricyclo [5,2,1,0] decane, 1, 3-diaminoadamantane, 2-bis (4-aminocyclohexyl) propane, 2-bis (4-aminocyclohexyl) hexafluoropropane, 1, 3-propane diamine, 1, 4-tetramethylene diamine, 1, 5-pentamethylene diamine, 1, 6-hexamethylenediamine, 1, 7-heptamethylene diamine, 1, 8-octamethylene diamine, and 1, 9-nonamethylene diamine.
The embodiment of the application also provides a preparation method of the polybenzoxazole precursor, which comprises the following steps:
s1: dissolving diamine monomer in a first solvent to obtain diamine monomer solution, wherein the mole percentage of diamine compounds shown in the formula (1) and/or the formula (2) in the diamine monomer is 10% -100%;
s2: and adding a dicarboxylic acid monomer shown in the formula (3) into the diamine monomer solution, and performing polymerization reaction to obtain a polybenzoxazole precursor solution.
In some embodiments, in step S1, the first solvent is selected from at least one of N-methylpyrrolidone, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone, tetrahydrofuran, 1, 3-dimethyl-2-imidazolidinone (DMI), γ -butyrolactone, ethyl acetate, butyl acetate, N-propyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, toluene, xylene, mesitylene, diacetone alcohol, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, methyl propyl ketone, tetrahydrofuran, tetrahydropyran, dioxane, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate.
In some preferred embodiments, step S2 satisfies one of the following conditions: 1) Adding dicarboxylic acid monomers shown in the formula (3) under the ice bath condition of 0-10 ℃, wherein the polymerization reaction temperature is 0-35 ℃ and the polymerization reaction time is 2-10 hours; 2) The molar ratio of the diamine monomer to the dicarboxylic acid monomer represented by the formula (3) is 1 (0.5-1).
In some embodiments, the method of preparing further comprises step S3: adding a blocking agent into the polybenzoxazole precursor solution to perform a blocking reaction to obtain a blocked polybenzoxazole precursor solution, wherein the molar ratio of the blocking agent to the diamine monomer is (0.02-0.2): 1, the temperature of the blocking reaction is 10-35 ℃ and the time is 1-4 hours; preferably, the end-capping agent is selected from at least one of phthalic anhydride, maleic anhydride, succinic anhydride, 2, 3-pyrazinedicarboxylic anhydride, tetrafluorophthalic anhydride, 2, 3-naphthalenedicarboxylic anhydride, hexahydrophthalic anhydride, norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, 4-phenylalkynylphthalic anhydride, bicyclo [2.2.2] oct-5-ene-2, 3-dicarboxylic anhydride, phenylsuccinic anhydride, 2' -biphenyldicarboxylic anhydride.
In some embodiments, the method of preparing further comprises step S4: dripping the polybenzoxazole precursor solution or the end-capped polybenzoxazole precursor solution into deionized water, and washing and drying the precipitate to obtain the dried polybenzoxazole precursor. In some embodiments, the cleaning liquid for cleaning the solid resin may be selected from at least one of distilled water, methanol, ethanol, isopropanol, and the like. The drying may be performed by at least one of a forced air oven, a vacuum oven, a freeze dryer, a fluidized dryer, and the like.
The embodiment of the application also provides a photosensitive resin composition which comprises the polybenzoxazole precursor with the cyclohexyl side group and a photosensitizer. The use of the above polybenzoxazole precursor having a cyclohexyl side group as a photosensitive polymer can significantly reduce the curing temperature of the photosensitive resin composition. When the photosensitive resin composition is applied to a black matrix, the performance of the black matrix can be improved.
In some embodiments, the photosensitive resin composition may further include other polybenzoxazole precursors in addition to the above-described polybenzoxazole precursors having a cyclohexyl side group.
In some preferred embodiments, the polybenzoxazole precursor having a cyclohexyl side group in the photosensitive resin composition accounts for 50 to 99% of the total mass of the nonvolatile components, and more preferably, 60 to 99%.
In some embodiments, the photosensitive agent is preferably 5 to 40 parts by weight, more preferably 10 to 30 parts by weight, based on 100 parts by weight of the polybenzoxazole precursor having a cyclohexyl side group in the photosensitive resin composition.
In some embodiments, the photosensitizer includes a photoacid generator and/or a photobase generator, or the like. In order to further improve the resolution, the sensitizer is preferably a photoacid generator. The photoacid generator is a compound that generates an acid by light irradiation of ultraviolet rays, visible light, or the like, and includes at least one of naphthoquinone diazide compounds, diaryl sulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryl iodonium salts, aryl diazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, nitrobenzyl esters, aromatic N-oxyimide sulfonic acid esters, aromatic sulfonamides, and benzoquinone diazonium sulfonic acid esters, as an example. Further preferably, the photoacid generator is a naphthoquinone diazide compound. The naphthoquinone diazide compound may be, for example, a naphthoquinone diazide adduct of tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene (for example, TS533, TS567, TS583, TS593, made by Mitsubao chemical research, inc.), a naphthoquinone diazide adduct of tetrahydroxybenzophenone (for example, BS550, BS570, BS599, made by Mitsubao chemical research, inc.), a naphthoquinone diazide adduct of 4- {4- [1, 1-bis (4-hydroxyphenyl) ethyl ] - α, α -dimethylbenzyl } phenol (for example, TKF-428, TKF-528, made by Mitsubao chemical research, inc.), or the like.
The photobase generator is a compound that generates one or more alkaline substances (secondary amine, tertiary amine, etc.) by changing the molecular structure or splitting the molecule by irradiation with ultraviolet light, visible light, etc. The photobase generator may be an ionic photobase generator or a nonionic photobase generator. In order to further improve the sensitivity of the photosensitive resin composition, the photobase generator is preferably an ionic photobase generator. Examples of the ionic photobase generator include salts of carboxylic acids and tertiary amines containing aromatic components, and examples of the commercial products include WPBG-082, WPBG-167, WPBG-168, WPBG-266, and WPBG-300, which are commercially available from Wako pure chemical industries, ltd. Examples of the nonionic photobase generator include an α -aminoacetophenone compound, an oxime ester compound, a compound having a substituent such as an N-formylated aromatic amino group, an N-acylated aromatic amino group, a nitrobenzyl carbamate group, and an alkoxybenzyl carbamate group. As other photobase generators, WPBG-018 (trade name: 9-tetrahydroxymethyl N, N' -diethyl arbamate), WPBG-027 (trade name: E) -1- [3- (2-hydroxyphenyl) -2-propenyl ] piperidine, WPBG-140 (trade name: 1- (antimicrobial-2-yl) ethyl imidazolecarboxylate) and WPBG-165, etc. manufactured by Wako pure chemical industries, ltd.
In some embodiments, the photosensitive resin composition may further include a crosslinking agent. The addition of the crosslinking agent can further sufficiently cure the photosensitive resin composition under low-temperature curing conditions. In some preferred embodiments, in the photosensitive resin composition, the polybenzoxazole precursor having a cyclohexyl side group is 100 parts by weight, and the crosslinking agent is preferably 0.1 to 30 parts by weight, and more preferably 0.1 to 20 parts by weight.
The crosslinking agent is preferably at least one compound capable of forming a crosslinked structure by reacting with a phenolic hydroxyl group in the polybenzoxazole precursor, for example, a crosslinking agent having a cyclic ether group such as an epoxy group, a cyclic thioether group such as an episulfide group, a crosslinking agent having an alcoholic hydroxyl group obtained by bonding an alkylene group having 1 to 12 carbon atoms such as a hydroxymethyl group to a hydroxyl group, a compound having an ether bond such as an alkoxymethyl group, a crosslinking agent having a triazine ring structure, a urea-based crosslinking agent, or the like. Further preferably, the crosslinking agent is at least one of a crosslinking agent having a cyclic ether group, particularly an epoxy group, and a crosslinking agent having an alcoholic hydroxyl group, particularly a hydroxymethyl group to which a hydroxyl group is bonded.
In some preferred embodiments, the crosslinking agent comprises a crosslinking agent having an epoxy group that thermally reacts with the hydroxyl group of the polybenzoxazole precursor to form a crosslinked structure. The number of functional groups of the crosslinking agent having an epoxy group is preferably 2 to 4. The photosensitive resin composition can further lower the curing temperature by containing a crosslinking agent having an epoxy group. Among the crosslinking agents having an epoxy group, epoxy compounds having a naphthalene skeleton with a difunctional group number of not less are preferable, and not only can an insulating film having more excellent flexibility and chemical resistance be obtained, but also a low CTE in the opposite relationship with flexibility can be achieved, and warpage and crack occurrence of the insulating film can be suppressed. In addition, bisphenol a type epoxy compounds may be suitably used as the crosslinking agent in view of flexibility.
In some preferred embodiments, the crosslinking agent comprises a crosslinking agent having hydroxymethyl groups, preferably having more than 2 hydroxymethyl groups.
In some preferred embodiments, the photosensitive resin composition may further include a thermal acid generator in order to further promote the cyclization reaction of the polybenzoxazole precursor. In some preferred embodiments, the photosensitive resin composition may further include a sensitizer in order to improve photosensitivity. In some preferred embodiments, the photosensitive resin composition may further include a binder such as a silane coupling agent in order to further improve adhesion to a substrate. In some preferred embodiments, various organic or inorganic low-molecular or high-molecular compounds may be added to further improve the processing characteristics and various functionalities of the photosensitive resin composition. For example, surfactants, leveling agents, fine particles, and the like can be used. The fine particles include organic fine particles of polystyrene, polytetrafluoroethylene, and the like, and inorganic fine particles of silica, carbon, layered silicate, and the like. In addition, various colorants, fibers, and the like may be blended into the photosensitive resin composition.
In some embodiments, the photosensitive resin composition further comprises a second solvent. The second solvent is not limited in kind as long as each component can be dissolved, and includes, for example, at least one of N, N '-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N' -dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ -butyrolactone, α -acetyl- γ -butyrolactone, tetramethylurea, 1, 3-dimethyl-2-imidazolidinone, N-cyclohexyl-2-pyrrolidone, dimethylsulfoxide, hexamethylphosphoramide, pyridine, γ -butyrolactone, diethylene glycol monomethyl ether, and the like.
In some embodiments, in the photosensitive resin composition, the polybenzoxazole precursor having a cyclohexyl side group is 100 parts by weight and the second solvent is 30 to 10000 parts by weight.
The photosensitive resin composition can be used for preparing photoresist.
The present embodiment also provides a dry film, which is a resin layer formed by drying the photosensitive resin composition, and the thickness thereof is not particularly limited, and may be, for example, 0.1 μm to 150 μm, as determined according to practical applications. The coating method is not limited, and for example, spin coater, bar coater, blade coater, curtain coater, screen printer, etc. may be used, or spray coater may be used for spray coating, ink jet method, etc. The drying method may be air drying, thermal drying using an oven or a hot plate, vacuum drying, or the like. In addition, drying is preferably performed under conditions that do not cause ring closure of the polybenzoxazole precursor in the photosensitive resin composition. In some preferred embodiments, natural drying, air drying, or heat drying is performed at 70℃to 140℃for 1 minute to 30 minutes. In order to simplify the operation method, a hot plate is preferably used, and drying is performed for 1 to 20 minutes. Alternatively, the vacuum drying may be performed at room temperature for 20 minutes to 1 hour.
The embodiment of the application also provides a cured film, and the preparation method of the cured film comprises the following steps:
s10: exposing and developing the dry film to form a pattern film;
s20: and heating and curing the pattern film.
In step S10, the wavelength of the light source employed at the time of exposure may be the wavelength at which the photoacid generator is activated. Preferably, the maximum wavelength is 350nm to 450 nm. The exposure amount is determined by the film thickness and the like, and can be usually set to 10mJ/cm 2 ～10000mJ/cm 2 Preferably, the ratio is 50mJ/cm 2 ～3000mJ/cm 2 Within a range of (2). The exposure machine used for exposure may be a device equipped with a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, or the like, and irradiating ultraviolet rays in a range of 350nm to 450 nm.
For development, a known method for developing a photoresist, for example, a spin spray method, a paddle method, a dipping method accompanied by ultrasonic treatment, or the like can be used. The developer may be an aqueous solution of inorganic bases such as sodium hydroxide, sodium carbonate, sodium silicate, and aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, and quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. If necessary, a proper amount of a water-soluble organic solvent such as methanol, ethanol, or isopropanol, or a surfactant may be added to the aqueous solution.
After the pattern film is formed, the pattern film may be further cleaned with a rinse solution. The flushing liquid is at least one selected from distilled water, methanol, ethanol, isopropanol and the like.
In step S20, the polybenzoxazole precursor is subjected to a cyclization reaction by heating to obtain polybenzoxazole. The heating condition can be 220-350 ℃ for 5-120 minutes. For heating, a hot plate, an oven, or a temperature-raising oven capable of setting a temperature program may be used, and heating under an inert gas such as nitrogen or argon is preferable.
The technical solutions of the present application will be clearly and completely described below in connection with the embodiments of the present application. The reagents and starting materials used were purchased commercially, unless otherwise indicated. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
Example 1
Preparing a polybenzoxazole precursor:
(1) 12.600g of 3,3 '-diamino-4, 4' -dihydroxydiphenyl sulfone and 1.4900g of 2,2 '-diamino-4, 4' - (cyclohexyl-1, 1-diyl) diphenol are completely dissolved in 103.8900g of N, N-dimethylacetamide, and diamine monomer solution is obtained;
(2) Under the nitrogen atmosphere and the ice bath condition at the temperature of 5 ℃, 11.0625g of 4,4' -diacyl chloride diphenyl ether solid is poured into the diamine monomer solution, after the pouring is finished, the ice bath is removed, and the polybenzoxazole precursor solution is obtained after the reaction for 4 hours under the nitrogen atmosphere and the temperature of 25 ℃;
(3) Pouring 0.8200g of norbornene dianhydride solid into the polybenzoxazole precursor solution under nitrogen atmosphere at 25 ℃ to react for 2 hours for end-capping reaction;
(4) And uniformly dripping the end-capped product system into deionized water, filtering, replacing the deionized water, soaking, washing again, filtering, repeating for a plurality of times, and drying to obtain the dried polybenzoxazole precursor containing the cyclohexyl side group.
Preparation of photosensitive resin composition:
10g of the polybenzoxazole precursor prepared in this example, 2g of naphthoquinone diazide adduct of TS533 (tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, sanbao chemical), 0.5g of gamma-glycidoxypropyl trimethoxysilane and 18g N-methylpyrrolidone were taken and stirred uniformly to obtain a photosensitive resin composition.
Example 2
Preparing a polybenzoxazole precursor:
(1) 12.600g of 3,3 '-diamino-4, 4' -dihydroxydiphenyl sulfone and 1.4900g of 2,2 '-diamino-4, 4' - (cyclohexyl-1, 1-diyl) diphenol are completely dissolved in 106.8400g of N, N-dimethylacetamide, and diamine monomer solution is obtained;
(2) Under the nitrogen atmosphere and the ice bath condition at the temperature of 5 ℃, 11.8000g of 4,4' -diacyl chloride diphenyl ether solid is poured into the diamine monomer solution, after the pouring is finished, the ice bath is removed, and the polybenzoxazole precursor solution is obtained after the reaction for 4 hours under the nitrogen atmosphere and the temperature of 25 ℃;
(3) Pouring 0.8200g of norbornene dianhydride solid into the polybenzoxazole precursor solution under nitrogen atmosphere at 25 ℃ to react for 2 hours for end-capping reaction;
(4) And uniformly dripping the end-capped product system into deionized water, filtering, replacing the deionized water, soaking, washing again, filtering, repeating for a plurality of times, and drying to obtain the dried polybenzoxazole precursor containing the cyclohexyl side group.
Preparation of photosensitive resin composition:
10g of the polybenzoxazole precursor prepared in this example, 2g of naphthoquinone diazide adduct of TS533 (tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, sanbao chemical), 0.5g of gamma-glycidoxypropyl trimethoxysilane and 18g N-methylpyrrolidone were taken and stirred uniformly to obtain a photosensitive resin composition.
Example 3
Preparing a polybenzoxazole precursor:
(1) 12.600g of 3,3 '-diamino-4, 4' -dihydroxydiphenyl sulfone and 1.4900g of 2,2 '-diamino-4, 4' - (cyclohexyl-1, 1-diyl) diphenol are completely dissolved in 109.7900g of N, N-dimethylacetamide, and diamine monomer solution is obtained;
(2) Under the nitrogen atmosphere and the ice bath condition at the temperature of 5 ℃, 12.5375g of 4,4' -diacyl chloride diphenyl ether solid is poured into the diamine monomer solution, after the pouring is finished, the ice bath is removed, and the polybenzoxazole precursor solution is obtained after the reaction for 4 hours under the nitrogen atmosphere and the temperature of 25 ℃;
(3) Pouring 0.8200g of norbornene dianhydride solid into the polybenzoxazole precursor solution under nitrogen atmosphere at 25 ℃ to react for 2 hours for end-capping reaction;
(4) And uniformly dripping the end-capped product system into deionized water, filtering, replacing the deionized water, soaking, washing again, filtering, repeating for a plurality of times, and drying to obtain the dried polybenzoxazole precursor containing the cyclohexyl side group.
Preparation of photosensitive resin composition:
10g of the polybenzoxazole precursor prepared in this example, 2g of naphthoquinone diazide adduct of TS533 (tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, sanbao chemical), 0.5g of gamma-glycidoxypropyl trimethoxysilane and 18g N-methylpyrrolidone were taken and stirred uniformly to obtain a photosensitive resin composition.
Example 4
Preparing a polybenzoxazole precursor:
(1) 11.200g of 3,3 '-diamino-4, 4' -dihydroxydiphenyl sulfone and 2.9800g of 2,2 '-diamino-4, 4' - (cyclohexyl-1, 1-diyl) diphenol are completely dissolved in 104.2500g of N, N-dimethylacetamide, and diamine monomer solution is obtained;
(2) Under the nitrogen atmosphere and the ice bath condition at the temperature of 5 ℃, 11.0625g of 4,4' -diacyl chloride diphenyl ether solid is poured into the diamine monomer solution, after the pouring is finished, the ice bath is removed, and the polybenzoxazole precursor solution is obtained after the reaction for 4 hours under the nitrogen atmosphere and the temperature of 25 ℃;
(3) Pouring 0.8200g of norbornene dianhydride solid into the polybenzoxazole precursor solution under nitrogen atmosphere at 25 ℃ to react for 2 hours for end-capping reaction;
(4) And uniformly dripping the end-capped product system into deionized water, filtering, replacing the deionized water, soaking, washing again, filtering, repeating for a plurality of times, and drying to obtain the dried polybenzoxazole precursor containing the cyclohexyl side group.
Preparation of photosensitive resin composition:
10g of the polybenzoxazole precursor prepared in this example, 2g of naphthoquinone diazide adduct of TS533 (tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, sanbao chemical), 0.5g of gamma-glycidoxypropyl trimethoxysilane and 18g N-methylpyrrolidone were taken and stirred uniformly to obtain a photosensitive resin composition.
Example 5
Preparing a polybenzoxazole precursor:
(1) 11.200g of 3,3 '-diamino-4, 4' -dihydroxydiphenyl sulfone and 2.9800g of 2,2 '-diamino-4, 4' - (cyclohexyl-1, 1-diyl) diphenol are completely dissolved in 107.2000g of N, N-dimethylacetamide, and diamine monomer solution is obtained;
(2) Under the nitrogen atmosphere and the ice bath condition at the temperature of 5 ℃, 11.8000g of 4,4' -diacyl chloride diphenyl ether solid is poured into the diamine monomer solution, after the pouring is finished, the ice bath is removed, and the polybenzoxazole precursor solution is obtained after the reaction for 4 hours under the nitrogen atmosphere and the temperature of 25 ℃;
(3) Pouring 0.8200g of norbornene dianhydride solid into the polybenzoxazole precursor solution under nitrogen atmosphere at 25 ℃ to react for 2 hours for end-capping reaction;
(4) And uniformly dripping the end-capped product system into deionized water, filtering, replacing the deionized water, soaking, washing again, filtering, repeating for a plurality of times, and drying to obtain the dried polybenzoxazole precursor containing the cyclohexyl side group.
Preparation of photosensitive resin composition:
10g of the polybenzoxazole precursor prepared in this example, 2g of naphthoquinone diazide adduct of TS533 (tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, sanbao chemical), 0.5g of gamma-glycidoxypropyl trimethoxysilane and 18g N-methylpyrrolidone were taken and stirred uniformly to obtain a photosensitive resin composition.
Example 6
Preparing a polybenzoxazole precursor:
(1) 11.200g of 3,3 '-diamino-4, 4' -dihydroxydiphenyl sulfone and 2.9800g of 2,2 '-diamino-4, 4' - (cyclohexyl-1, 1-diyl) diphenol are completely dissolved in 110.1500g of N, N-dimethylacetamide, and diamine monomer solution is obtained;
(2) Under the nitrogen atmosphere and the ice bath condition at the temperature of 5 ℃, 12.5375g of 4,4' -diacyl chloride diphenyl ether solid is poured into the diamine monomer solution, after the pouring is finished, the ice bath is removed, and the polybenzoxazole precursor solution is obtained after the reaction for 4 hours under the nitrogen atmosphere and the temperature of 25 ℃;
(3) Pouring 0.8200g of norbornene dianhydride solid into the polybenzoxazole precursor solution under nitrogen atmosphere at 25 ℃ to react for 2 hours for end-capping reaction;
(4) And uniformly dripping the end-capped product system into deionized water, filtering, replacing the deionized water, soaking, washing again, filtering, repeating for a plurality of times, and drying to obtain the dried polybenzoxazole precursor containing the cyclohexyl side group.
Preparation of photosensitive resin composition:
10g of the polybenzoxazole precursor prepared in this example, 2g of naphthoquinone diazide adduct of TS533 (tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, sanbao chemical), 0.5g of gamma-glycidoxypropyl trimethoxysilane and 18g N-methylpyrrolidone were taken and stirred uniformly to obtain a photosensitive resin composition.
Example 7
Preparing a polybenzoxazole precursor:
(1) 12.8100g of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4.4700g of 2,2 '-diamino-4, 4' - (cyclohexyl-1, 1-diyl) diphenol were completely dissolved in 116.6500g of N, N-dimethylacetamide to obtain a diamine monomer solution;
(2) Under the nitrogen atmosphere and the ice bath condition at the temperature of 5 ℃, 11.0625g of 4,4' -diacyl chloride diphenyl ether solid is poured into the diamine monomer solution, after the pouring is finished, the ice bath is removed, and the polybenzoxazole precursor solution is obtained after the reaction for 4 hours under the nitrogen atmosphere and the temperature of 25 ℃;
(3) Pouring 0.8200g of norbornene dianhydride solid into the polybenzoxazole precursor solution under nitrogen atmosphere at 25 ℃ to react for 2 hours for end-capping reaction;
(4) And uniformly dripping the end-capped product system into deionized water, filtering, replacing the deionized water, soaking, washing again, filtering, repeating for a plurality of times, and drying to obtain the dried polybenzoxazole precursor containing the cyclohexyl side group.
Preparation of photosensitive resin composition:
10g of the polybenzoxazole precursor prepared in this example, 2g of naphthoquinone diazide adduct of TS533 (tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, sanbao chemical), 0.5g of gamma-glycidoxypropyl trimethoxysilane and 18g N-methylpyrrolidone were taken and stirred uniformly to obtain a photosensitive resin composition.
The photosensitive resin composition prepared in example 7 was coated and baked to prepare a dry film, and was cured at a low temperature for 1 hour in an oxygen-free atmosphere having an oxygen content of less than 100ppm at 250℃to obtain a cured PBO film. The PBO film was subjected to fourier transform infrared spectroscopy (FT-IR) testing: the sample iS tested by adopting a Nicolet iS5 type Fourier infrared spectrometer of ThermoFisher technology Co, and the test range covers 4000-500 cm -1 The test times were set to 32 timesThe sample was placed directly on the ATR unit at the time of the test, and the FT-IR diagram shown in fig. 3 was obtained. As shown in FIG. 3, 1052cm -1 The C-O bond on the oxazole ring stretches out and draws back the vibration peak, but 1539cm -1 The peak of the amide bond at the site had disappeared, demonstrating that the PBO membrane had been substantially cyclized.
Example 8
Preparing a polybenzoxazole precursor:
(1) 12.8100g of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4.4700g of 2,2 '-diamino-4, 4' - (cyclohexyl-1, 1-diyl) diphenol were completely dissolved in 119.6000g of N, N-dimethylacetamide to obtain a diamine monomer solution;
(2) Under the nitrogen atmosphere and the ice bath condition at the temperature of 5 ℃, 11.8000g of 4,4' -diacyl chloride diphenyl ether solid is poured into the diamine monomer solution, after the pouring is finished, the ice bath is removed, and the polybenzoxazole precursor solution is obtained after the reaction for 4 hours under the nitrogen atmosphere and the temperature of 25 ℃;
(3) Pouring 0.8200g of norbornene dianhydride solid into the polybenzoxazole precursor solution under nitrogen atmosphere at 25 ℃ to react for 2 hours for end-capping reaction;
(4) And uniformly dripping the end-capped product system into deionized water, filtering, replacing the deionized water, soaking, washing again, filtering, repeating for a plurality of times, and drying to obtain the dried polybenzoxazole precursor containing the cyclohexyl side group.
Preparation of photosensitive resin composition:
10g of the polybenzoxazole precursor prepared in this example, 2g of naphthoquinone diazide adduct of TS533 (tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, sanbao chemical), 0.5g of gamma-glycidoxypropyl trimethoxysilane and 18g N-methylpyrrolidone were taken and stirred uniformly to obtain a photosensitive resin composition.
Example 9
Preparing a polybenzoxazole precursor:
(1) 12.8100g of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4.4700g of 2,2 '-diamino-4, 4' - (cyclohexyl-1, 1-diyl) diphenol were completely dissolved in 122.5500g of N, N-dimethylacetamide to obtain a diamine monomer solution;
(2) Under the nitrogen atmosphere and the ice bath condition at the temperature of 5 ℃, 12.5375g of 4,4' -diacyl chloride diphenyl ether solid is poured into the diamine monomer solution, after the pouring is finished, the ice bath is removed, and the polybenzoxazole precursor solution is obtained after the reaction for 4 hours under the nitrogen atmosphere and the temperature of 25 ℃;
(3) Pouring 0.8200g of norbornene dianhydride solid into the polybenzoxazole precursor solution under nitrogen atmosphere at 25 ℃ to react for 2 hours for end-capping reaction;
(4) And uniformly dripping the end-capped product system into deionized water, filtering, replacing the deionized water, soaking, washing again, filtering, repeating for a plurality of times, and drying to obtain the dried polybenzoxazole precursor containing the cyclohexyl side group.
Preparation of photosensitive resin composition:
10g of the polybenzoxazole precursor prepared in this example, 2g of naphthoquinone diazide adduct of TS533 (tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, sanbao chemical), 0.5g of gamma-glycidoxypropyl trimethoxysilane and 18g N-methylpyrrolidone were taken and stirred uniformly to obtain a photosensitive resin composition.
Weight average molecular weight (Mw) and molecular weight distribution index (PDI) measurements
The polybenzoxazole precursors prepared in examples 1 to 9 were examined for weight average molecular weight (Mw) and molecular weight distribution index (PDI) by Gel Permeation Chromatography (GPC). The testing method comprises the following steps: filling a chromatographic column with DMAc to occupy all gaps among carrier particles and cavities in the particles, adding a sample solution prepared by the same solvent from a column head, eluting by the same solvent, collecting the eluting liquid at the micro end of the chromatographic column, calculating the volume and the concentration of the eluting liquid, and calling the total volume of the received eluting liquid as the eluting volume. The leached volume of solute is related to its molecular weight, and the larger the molecular weight, the smaller the leached volume. If the sample is polydisperse, a series of fractions of molecular weight ranging from large to small can be collected in the order of leaching. The test results are shown in Table 1.
TABLE 1 Mw and PDI of polybenzoxazole precursors prepared in examples 1-9
Group of Mw PDI
Example 1 10159 1.47
Example 2 13229 1.66
Example 3 16795 1.78
Example 4 10942 1.49
Example 5 14117 1.68
Example 6 18096 1.85
Example 7 11439 1.54
Example 8 14796 1.70
Example 9 19007 1.89
Lithographic performance test
The photosensitive resin compositions prepared in examples 1 and 2 were subjected to pressure filtration to remove insoluble matters, and defoamed under vacuum to obtain a photosensitive resin composition solution, which was spin-coated on a silicon wafer, and then placed on a hot plate at 120 ℃ for pre-baking for 180s, and most of the solvent was volatilized to obtain a dry film. Exposing the dry film by using a stepping photoetching machine (SSB 320) with the exposure of 400-1200 mJ/cm 2 Development was performed with 2.38% by mass aqueous TMAH (tetramethylammonium hydroxide) for 30s x 2 times and the pattern was observed under a microscope.
The patterns after development by exposure using the photosensitive resin compositions of example 1 and example 2 are shown in fig. 4 and 5, respectively. As can be seen from the figures, the photosensitive resin compositions prepared in examples 1 and 2 were used to prepare patterns (10 μm@10μm, i.e., 10 μm openings with a film thickness of 10 μm) having high resolution.
Example 10
The photosensitive resin composition prepared in example 1 was subjected to film coating, baking, exposure, and development to prepare dumbbell-shaped bars, which were cured at low temperature in an oxygen-free atmosphere having an oxygen content of less than 100ppm at 220℃for 1 hour, to obtain cured PBO bars.
Example 11
The photosensitive resin composition prepared in example 1 was subjected to film coating, baking, exposure, and development to prepare dumbbell-shaped bars, which were cured at low temperature for 1 hour in an oxygen-free atmosphere having an oxygen content of less than 100ppm at 250 ℃ to obtain cured PBO bars.
Example 12
The photosensitive resin composition prepared in example 1 was subjected to film coating, baking, exposure, and development to prepare dumbbell-shaped bars, which were cured at low temperature for 1 hour in an oxygen-free atmosphere having an oxygen content of less than 100ppm at 280 ℃, to obtain cured PBO bars.
Example 13
The photosensitive resin composition prepared in example 1 was subjected to film coating, baking, exposure, and development to prepare dumbbell-shaped bars, which were cured at low temperature for 1 hour in an oxygen-free atmosphere having an oxygen content of less than 100ppm at 300 ℃, to obtain cured PBO bars.
Example 14
The photosensitive resin composition prepared in example 1 was subjected to film coating, baking, exposure, and development to prepare dumbbell-shaped bars, which were cured at low temperature for 1 hour in an oxygen-free atmosphere having an oxygen content of less than 100ppm at 320 ℃, to obtain cured PBO bars.
Comparative example 1
The photosensitive resin composition prepared in example 1 was subjected to film coating, baking, exposure, and development to prepare dumbbell-shaped bars, which were cured at low temperature for 1 hour in an oxygen-free atmosphere having an oxygen content of less than 100ppm at high temperature 350 ℃ to obtain cured PBO bars.
The PBO bars of examples 10-15 and comparative example 1 were tested in attenuated total reflection mode using a ThermoFisher technology Co., ltd. Nicolet iS5 Fourier infrared spectrometer to verify the degree of cyclization. By measuring 1052cm -1 The cyclization ratio of the PBO membrane was monitored for the signal intensity of the c—o bond on the oxazole ring, and the cyclization ratio was 100% as the signal intensity of comparative example 1, to obtain the cyclization ratio shown in table 2. The cyclisation results show that the degree of cyclisation in the examples of the present application has been near complete solidification.
Mechanical property test
The tensile properties, thermal expansion coefficients and dynamic thermo-mechanical properties (DMA) of the PBO bars of examples 10 to 14 and comparative example 1 were tested, and the test results are shown in table 2.
Tensile property test: the tensile strength, young's modulus and elongation at break of the bars were characterized using a universal tensile machine of the type CMT-1104, mitsui electric equipments Co., ltd. In bead sea, the test was performed according to the Standard test method for Plastic tensile Property (ASTM-D638), and the stretching was performed at a stretching speed of 5mm/min until the bars break. The final data were averaged over 5 measurements.
TMA test: the Coefficient of Thermal Expansion (CTE) of the bars was characterized using a TA Instruments model Q400 static thermo-mechanical analyzer to determine their dimensional stability over the normal operating temperature range. In the stretching mode, the temperature was raised to 300℃in a nitrogen atmosphere at a temperature-raising rate of 30℃per minute and left for 5 minutes to eliminate residual thermal potential, followed by cooling to room temperature at the same rate, followed by a secondary temperature rise to 390℃at a temperature-raising rate of 5℃per minute. The static force is set to be 0.05N, and the final CTE value is 50-150 ℃.
DMA test: the glass transition temperature (Tg) of the bars was characterized using a dynamic thermo-mechanical analyzer model Q800 from TA Instruments ltd in the united states to determine their upper normal operating temperature limit. In the dynamic pull-up mode, the temperature was raised to 500℃in a nitrogen atmosphere at a temperature-raising rate of 5℃per minute, and the test frequency was set at 1Hz.
Table 2 mechanical properties test results for examples 10 to 14 and comparative example 1
2, the mechanical properties of the polymer in the embodiment of the application are similar to those of the polymer in the low-temperature (220 ℃ to 300 ℃) curing and the high-temperature (350 ℃) curing, which indicates that the polymer in the embodiment of the application can be cured at the low temperature and has excellent mechanical properties. The Tg of the polymers of the examples herein increased with increasing curing temperature, and all exceeded 250℃to meet the use requirements.
Thermal performance testing
The PBO splines of examples 10 to 14 and comparative example 1 were subjected to thermal re-testing by the following specific test methods:
stability of the instrumented materials was analyzed using a thermal gravimetric analysis model TGA55, incorporated by TA Instruments, USA. Weighing 10-15mg of sample, carefully placing in an alumina high-temperature crucible, heating to 120 ℃ at a heating rate of 20 ℃/min under nitrogen atmosphere, keeping for 10min to remove trace moisture contained in the sample, cooling to room temperature, heating to 800 ℃ at a heating rate of 10 ℃/min for a second time, and heating to a nitrogen pressure of not more than 0.1MPa. The test results are shown in Table 3.
Table 3 thermal performance test results for examples 10-14 and comparative example 1
Project Curing temperature Td1％(℃) Td3％(℃) Td5％(℃)
Example 10 220℃ 259.44 285.52 341.15
Example 11 250℃ 288.57 324.12 371.12
Example 12 280℃ 311.41 361.78 405.88
Example 13 300℃ 335.58 395.47 429.43
Example 14 320℃ 363.91 414.80 447.73
Comparative example 1 350℃ 401.07 445.29 476.71
Table 3 shows the thermal performance test results of the polybenzoxazole precursor containing a pendant cyclohexyl group prepared in example 1 at different curing temperatures. At curing temperatures of 220 ℃ to 350 ℃, td of the polybenzoxazole precursor increases with increasing curing temperature and both exceed 250 ℃. Therefore, the polybenzoxazole precursor prepared by the embodiment of the application has excellent thermal properties, and meets the use requirements.
Chemical corrosion resistance test
Example 15
The photosensitive resin composition of example 1 was spin-coated on a silicon wafer, and pre-baked on a hot plate at 120 ℃ for 180s, and most of the solvent was volatilized to obtain a dry film. Exposing the dry film by using a stepping photoetching machine (SSB 320) with the exposure of 400-1200 mJ/cm 2 Developing with 2.38% TMAH (tetramethylammonium hydroxide) aqueous solution for 30s for 2 times, and rinsing with leaching solution to obtain the final productA cured positive resin pattern. The silicon wafer with the uncured positive resin pattern was placed in a nitrogen-protected air-blast oven (oxygen concentration below 100 ppm) to be cured at 150 ℃ for 30min, and then heated to 220 ℃ to be cured for 1h, to obtain a cured film.
Example 16
The silicon wafer with the uncured positive resin pattern of example 15 was placed in a nitrogen-protected air-blown oven (oxygen concentration 100ppm or less) and cured at 150 ℃ for 30min, followed by heating to 250 ℃ and curing for 1h to obtain a cured film.
Example 17
The silicon wafer with the uncured positive resin pattern of example 15 was placed in a nitrogen-protected air-blown oven (oxygen concentration 100ppm or less) and cured at 150 ℃ for 30min, followed by heating to 280 ℃ and curing for 1h to obtain a cured film.
Example 18
The silicon wafer with the uncured positive resin pattern of example 15 was placed in a nitrogen-protected air-blown oven (oxygen concentration of 100ppm or less) to be cured at 150 ℃ for 30min, followed by heating to 300 ℃ to be cured for 1h, to obtain a cured film.
Example 19
The silicon wafer with the uncured positive resin pattern of example 15 was placed in a nitrogen-protected air-blown oven (oxygen concentration of 100ppm or less) to be cured at 150 ℃ for 30min, followed by heating to 320 ℃ to be cured for 1h, to obtain a cured film.
The silicon wafers with cured films obtained in examples 15 to 19 and PBO splines of comparative example 1 were subjected to the respective organic reagents of acetone (25 ℃ C., 60 s), ammonia (25 ℃ C., 60 s), HCl (25 ℃ C., 60 s), H 2 SO 4 And H 2 O 2 Soaking the mixture (25 ℃ for 180 seconds) and N-methylpyrrolidone (25 ℃ for 30 minutes), washing with water, drying by blowing, measuring the change of film thickness before and after soaking the silicon wafer with the solidified film by using a film thickness meter, observing patterns by using an optical microscope, and evaluating the chemical corrosion resistance of the silicon wafer.
The chemical resistance was evaluated as a for the film thickness change of not more than 5% before and after immersion, as B for the film thickness change of not more than 5% before and after immersion, and as C for the film surface crack, pattern corner crack, pattern edge chemical penetration or peeling of the cured film from the substrate, and the test results can be seen in table 4.
TABLE 4 results of chemical resistance test of examples 15 to 19 and comparative example 1
Project Curing temperature Acetone (acetone) Ammonia water HCl H 2 SO 4 /H 2 O 2 N-methyl pyrrolidone
Example 15 220℃ A A A A A
Example 16 250℃ A A A A A
Example 17 280℃ A A A A A
Example 18 300℃ A A A A A
Example 19 320℃ A A A A A
Comparative example 1 350℃ A A A A A
As can be seen from Table 4, the polybenzoxazole precursors containing pendant cyclohexyl groups prepared in the examples of this application have good chemical resistance.
Fig. 6 shows a 3D map of the film surface after soaking the cured film of example 16 in N-methyl pyrrolidone (25 ℃,30 min). As can be seen from fig. 6, the film surface was flat, no cracks were generated, and the cured film was proved to have excellent chemical resistance.
The embodiments are described above in order to facilitate the understanding and application of the present application by those of ordinary skill in the art. It will be apparent to those skilled in the art that various modifications can be made to these embodiments and that the general principles described herein may be applied to other embodiments without the use of inventive faculty. Accordingly, the present application is not limited to the embodiments herein, and those skilled in the art, based on the present disclosure, may make improvements and modifications without departing from the scope and spirit of the present application.

Claims (10)

1. A polybenzoxazole precursor formed by the reaction of a diamine monomer and a dicarboxylic acid monomer; wherein the diamine monomer comprises a diamine compound represented by formula (1) and/or formula (2):
in the formula (1) and the formula (2), R 1 ～R 5 、R 11 ～R 51 Independently selected from hydrogen or monovalent organic groups;
the dicarboxylic acid monomer has a structure represented by formula (3):
in formula (3), X is a divalent organic group that is an aliphatic group or an aromatic group; z is selected from hydroxyl or halogen groups.
2. According to claimThe polybenzoxazole precursor according to 1, wherein said monovalent organic group is selected from the group consisting of C1 to C12 alkyl groups, C1 to C12 alkoxy groups, C6 to C10 aromatic groups, C6 to C10 phenoxy groups, C6 to C10 benzyl groups and C6 to C10 benzyloxy groups; at R 1 ～R 5 In and R 11 ～R 51 Wherein 0 to 3 groups are independently selected from the monovalent organic groups, and the remaining groups are hydrogen; preferably, at R 1 ～R 5 In and R 11 ～R 51 Wherein each of the radicals is independently selected from the monovalent organic groups, the remaining radicals are hydrogen, or R 1 ～R 5 R is R 11 ～R 51 Are all hydrogen.
3. The polybenzoxazole precursor according to claim 1 wherein X is a C6 to C48 aromatic group; preferably, X is an aromatic group of C6-C24; further preferably, the X isWherein A is selected from the group consisting of single bond, alkylene, -O-, -and->-S-、/>-C(CF 3 ) 2 -and-C (CH) 3 ) 2 -, represents a linker to the carbonyl group in formula (3).
4. The polybenzoxazole precursor according to claim 1, wherein said dicarboxylic acid monomer is selected from at least one of aromatic dicarboxylic acid, aliphatic dicarboxylic acid, dihalide or dicarboxylic ester of said aromatic dicarboxylic acid, dihalide or dicarboxylic ester of said aliphatic dicarboxylic acid; preferably, the method comprises the steps of, the aromatic dicarboxylic acid is selected from isophthalic acid, terephthalic acid, 5-tert-butyl isophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2, 6-naphthalene dicarboxylic acid, 4' -dicarboxybiphenyl 4,4' -dicarboxydiphenyl ether, 4' -dicarboxydiphenyl silane, bis (4-carboxyphenyl) sulfone at least one of 2, 2-bis (p-carboxyphenyl) propane and 2, 2-bis (4-carboxyphenyl) -1, 3-hexafluoropropane; preferably, the aliphatic dicarboxylic acid is at least one selected from oxalic acid, malonic acid, succinic acid, 1, 2-cyclobutanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, and 1, 3-cyclopentanedicarboxylic acid.
5. The polybenzoxazole precursor according to any of claims 1 to 4 where the diamine monomer further comprises a diamine compound represented by formula (4):
H 2 N—Y-NH 2
formula (4);
in the formula (4), Y is a tetravalent organic group having at least two or more hydroxyl groups, the tetravalent organic group being an aliphatic group or an aromatic group; preferably, the tetravalent organic group is an aromatic group.
6. The polybenzoxazole precursor according to claim 5 where Y is selected from the following tetravalent organic groups:
wherein one of 1 and 2 represents a linking moiety with an amino group in formula (4), and the other represents a linking moiety with a hydroxyl group.
7. The polybenzoxazole precursor as defined in claim 6 wherein the polybenzoxazole precursor has a structural formula as shown in formula (I) or formula (II):
in the formula (I) and the formula (II), X isY is->
n and n1 are 1 to 100, m and m1 are 0 to 100; preferably, n and n1 are 1 to 40, and m1 are 15 to 40.
8. A process for preparing a polybenzoxazole precursor according to any one of claims 1 to 7 including the steps of:
s1: dissolving diamine monomer in a first solvent to obtain diamine monomer solution, wherein the mole percentage of diamine compounds shown in the formula (1) and/or the formula (2) in the diamine monomer is 10% -100%;
S2: and adding a dicarboxylic acid monomer shown in the formula (3) into the diamine monomer solution, and performing polymerization reaction to obtain a polybenzoxazole precursor solution.
9. The production method according to claim 8, wherein the first solvent is at least one selected from the group consisting of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, tetrahydrofuran, 1, 3-dimethyl-2-imidazolidinone, γ -butyrolactone, ethyl acetate, butyl acetate, N-propyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, toluene, xylene, mesitylene, diacetone alcohol, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, methyl propyl ketone, tetrahydrofuran, tetrahydropyran, dioxane, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate;
and/or, step S2 satisfies one of the following conditions: 1) Adding dicarboxylic acid monomers shown in the formula (3) under the ice bath condition of 0-10 ℃, wherein the polymerization reaction temperature is 0-35 ℃ and the polymerization reaction time is 2-10 hours; 2) The molar ratio of the diamine monomer to the dicarboxylic acid monomer shown in the formula (3) is 1 (0.5-1);
And/or, the preparation method further comprises the step S3: adding a blocking agent into the polybenzoxazole precursor solution to perform a blocking reaction to obtain a blocked polybenzoxazole precursor solution, wherein the molar ratio of the blocking agent to the diamine monomer is (0.02-0.2): 1, the temperature of the blocking reaction is 10-35 ℃ and the time is 1-4 hours; preferably, the end-capping agent is selected from at least one of phthalic anhydride, maleic anhydride, succinic anhydride, 2, 3-pyrazinedicarboxylic anhydride, tetrafluorophthalic anhydride, 2, 3-naphthalenedicarboxylic anhydride, hexahydrophthalic anhydride, norbornenedicarboxylic anhydride, tetrahydrophthalic anhydride, 4-phenylalkynylphthalic anhydride, bicyclo [2.2.2] oct-5-ene-2, 3-dicarboxylic anhydride, phenylsuccinic anhydride, 2' -biphenyldicarboxylic anhydride;
and/or, the preparation method further comprises the step S4: dripping the polybenzoxazole precursor solution or the end-capped polybenzoxazole precursor solution into deionized water, and washing and drying the precipitate to obtain the dried polybenzoxazole precursor.
10. A photosensitive resin composition is characterized by comprising the following components in parts by weight: 100 parts of the polybenzoxazole precursor according to any of claims 1 to 7, 5 to 40 parts of a sensitizer and 30 to 10000 parts of a second solvent; preferably, the photosensitizer comprises at least one of photoacid generator, photobase generator, crosslinking agent, thermal acid generator, sensitizer, thickener, surfactant, leveling agent, and fine particles; preferably, the second solvent includes at least one of N, N '-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N' -dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ -butyrolactone, α -acetyl- γ -butyrolactone, tetramethylurea, 1, 3-dimethyl-2-imidazolidinone, N-cyclohexyl-2-pyrrolidone, dimethylsulfoxide, hexamethylphosphoramide, pyridine, γ -butyrolactone, and diethylene glycol monomethyl ether.
CN202311742221.1A 2023-12-18 2023-12-18 Polybenzoxazole precursor, process for producing the same, and photosensitive resin composition Pending CN117866200A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311742221.1A CN117866200A (en) 2023-12-18 2023-12-18 Polybenzoxazole precursor, process for producing the same, and photosensitive resin composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311742221.1A CN117866200A (en) 2023-12-18 2023-12-18 Polybenzoxazole precursor, process for producing the same, and photosensitive resin composition

Publications (1)

Publication Number Publication Date
CN117866200A true CN117866200A (en) 2024-04-12

Family

ID=90578061

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311742221.1A Pending CN117866200A (en) 2023-12-18 2023-12-18 Polybenzoxazole precursor, process for producing the same, and photosensitive resin composition

Country Status (1)

Country Link
CN (1) CN117866200A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999017366A1 (en) * 1997-09-29 1999-04-08 Siemens Aktiengesellschaft Semiconductor component and method for the production thereof
JP2008233363A (en) * 2007-03-19 2008-10-02 Fujifilm Corp Photosensitive resin composition, method for making cured relief pattern using the same and semiconductor device
JP2010139929A (en) * 2008-12-15 2010-06-24 Toyobo Co Ltd Positive photosensitive polyimide resin composition
CN101827880A (en) * 2007-12-26 2010-09-08 旭化成电子材料株式会社 Precursor for heat-resistant resin and photosensitive resin composition containing the same
JP2019183122A (en) * 2018-03-30 2019-10-24 東レ株式会社 Photosensitive resin composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999017366A1 (en) * 1997-09-29 1999-04-08 Siemens Aktiengesellschaft Semiconductor component and method for the production thereof
JP2008233363A (en) * 2007-03-19 2008-10-02 Fujifilm Corp Photosensitive resin composition, method for making cured relief pattern using the same and semiconductor device
CN101827880A (en) * 2007-12-26 2010-09-08 旭化成电子材料株式会社 Precursor for heat-resistant resin and photosensitive resin composition containing the same
JP2010139929A (en) * 2008-12-15 2010-06-24 Toyobo Co Ltd Positive photosensitive polyimide resin composition
JP2019183122A (en) * 2018-03-30 2019-10-24 東レ株式会社 Photosensitive resin composition

Similar Documents

Publication Publication Date Title
KR101965053B1 (en) Tetracarboxylic acid diester compound, polyimide precursor polymer and method for producing the same, negative photosensitive resin composition, positive photosensitive resin composition, patterning process, and method for forming cured film
JP4618075B2 (en) Negative photosensitive resin composition and pattern forming method
JP7059927B2 (en) Resin compositions, resin sheets, curing patterns and semiconductor electronic components or semiconductor devices
JP4923656B2 (en) Negative photosensitive resin composition, pattern manufacturing method, and electronic component
US20090181224A1 (en) Negative-type photosensitive resin composition, pattern forming method and electronic parts
KR102015098B1 (en) Polyimide resin and positive photosensitive resin composition
KR20190083329A (en) Diamine compounds, heat-resistant resins using them, and resin compositions
CN109153841B (en) Resin composition
CN114995061B (en) Low-water-absorption positive photosensitive resin composition and preparation method and application thereof
CN115220305A (en) Positive photosensitive resin composition and preparation method and application thereof
JP5076390B2 (en) Negative photosensitive resin composition, method for producing patterned cured film, and electronic component
TW201335703A (en) Photosensitive resin composition, manufacturing method of cured film pattern and electronic component
JP5099979B2 (en) Negative photosensitive resin composition, pattern manufacturing method, and electronic component
CN114488690A (en) Chemical amplification type negative polyimide photoresist and preparation method and application thereof
JP5109471B2 (en) Negative photosensitive resin composition, pattern manufacturing method, and electronic component
CN108473679B (en) Cured film and method for producing same
JP5895749B2 (en) Resin composition, method for producing patterned resin film, polymer, and semiconductor device
TWI692490B (en) Hardened film and its manufacturing method
CN113518792B (en) Polybenzoxazole precursor containing ester diamine, photosensitive resin composition, dry film, cured product, and electronic component
CN117866200A (en) Polybenzoxazole precursor, process for producing the same, and photosensitive resin composition
JP2006178059A (en) Negative photosensitive resin composition, method for producing pattern and electronic component
CN117534836B (en) Polybenzoxazole precursor, process for producing the same, and photosensitive resin composition
JP7155471B2 (en) Positive photosensitive composition and method for producing photosensitive composition
CN118092074B (en) Chemical amplification type positive photosensitive polyimide coating adhesive and preparation method and application thereof
TWI830255B (en) Photosensitive polyimide resin composition

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