CN115160569A - Photosensitive polyamic acid ester resin, resin composition and electronic component - Google Patents
Photosensitive polyamic acid ester resin, resin composition and electronic component Download PDFInfo
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/128—Unsaturated polyimide precursors the unsaturated precursors containing heterocyclic moieties in the main chain
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- 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
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- G03F7/004—Photosensitive materials
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- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0387—Polyamides or polyimides
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- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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Abstract
The invention discloses a photosensitive polyamic acid ester resin, a resin composition and an electronic component. The structural formula of the photosensitive polyamic acid ester resin is shown as a formula I. According to the invention, the photosensitive polyamic acid ester resin is prepared from the fluorine-containing aromatic dianhydride, the aromatic diamine containing benzoxazole group, the aromatic diamine and the esterifying reagent, and the polyimide film obtained by thermal imidization has the characteristics of high temperature resistance, high modulus, low thermal expansion and the like, and has the characteristic of low dielectric constant, and meanwhile, due to the introduction of fluorine atoms, the transparency of the polyimide film is improved, so that the film has excellent i-ray transmittance and the resolution is improved; introduction of benzoxazole groups allowsThe Tg of PI is more than 300 ℃, and the modulus of more than 1GPa can be maintained at the high temperature of 260 ℃; the patterned resin film can be easily formed by introducing a photosensitive group into the polyimide precursor by an esterification agent.
Formula I.
Description
Technical Field
The invention belongs to the technical field of polymers, and relates to a photosensitive polyamic acid ester resin with low dielectric loss, high temperature resistance, high strength, high modulus and low thermal expansion, a resin composition and an electronic component.
Background
With the continuous upgrading and upgrading of electronic products, emerging markets such as smart phones, 5G and AI set higher requirements for packaging technology, so that the packaging technology develops towards high integration, three-dimensional, ultrafine pitch interconnection and the like. The wafer level packaging technology can reduce the size of a chip, the wiring length, the solder ball distance and the like, so that the integration level of an integrated circuit, the speed of a processor and the like can be improved, the power consumption is reduced, the reliability is improved, and the development requirements of increasingly light, thin, short, small and low cost of electronic products are met.
A Redistribution Layer (RDL) is a key part of the wafer level packaging technology. The rewiring layer is formed by coating a layer of polyimide resin composition on the IC, defining a new wire pattern in an exposure and development mode, forming an insulating protective layer after curing, and then manufacturing a new metal circuit by utilizing an electroplating technology to connect the original aluminum pad and a new bump so as to achieve the purpose of redistribution of the circuit. The electronic components passing through the rewiring layer are connected to the PCB panel using a reflow process. When an electronic component is subjected to high-temperature (245-260 ℃) reflow soldering, tin at the end is melted, the modulus of a dielectric film below a tin ball is required to be maintained at the high temperature of 260 ℃ for more than 1GPa, otherwise, the melted tin flows at the layering position of the dielectric film, so that the whole product fails, most film materials on the market have high normal-temperature modulus, but the modulus of the film materials at the high temperature of 260 ℃ cannot be maintained at the high temperature of 1 GPa.
The excellent properties of high heat resistance, high strength and high modulus, low thermal expansion and high adhesion of Polyimide (PI) enable the polyimide to be widely applied in the technical field of electronics. With the rapid development of the microelectronics industry, the miniaturization and integration of integrated circuits has led to smaller and smaller chip sizes. Due to the reduction of the distance between the internal components of the chip, the performance of the chip is greatly reduced by the delay of signal transmission, and the development requirement of information processing on high frequency and high speed of signal transmission is met, so that the requirements on the heat resistance of the material are not low, and the requirements on the low dielectric constant and low dielectric loss of the material are more and more strict, so that the development of an insulating layer with a low dielectric constant is very important. Hoyle et al (C. E. Hoyle, D. Creed, P. Subramian. Polymer Prep, 1993, 34. This is because the introduction of fluorine atoms into the main chain structure of the PI resin reduces the electron polarization effect, and as the fluorine content increases, the free volume fraction of the system increases, resulting in a linear decrease in the dielectric constant. However, perfluorinated polyimides can cause a decrease in the glass transition temperature and mechanical properties of the polymer and an increase in the coefficient of thermal expansion. As a means for reducing the dielectric constant, a method using an alicyclic polyimide has been proposed (patent document 1: japanese patent application laid-open No. 2009-186861). By utilizing the low dielectric constant of air (close to 1), nanometer-scale holes are introduced into the polyimide film material, the dielectric constant of the material can be effectively reduced (patent document 2.
Disclosure of Invention
The purpose of the present invention is to provide a photosensitive polyamic acid ester resin, a resin composition, and an electronic component, wherein a polyimide film obtained by thermal imidization of the photosensitive polyamic acid ester resin has not only high temperature resistance, high modulus, low thermal expansion and other properties, but also low dielectric constant (Dk < 2.5) and low dielectric loss (Df < 0.006), excellent i-line transmittance, and can maintain a modulus of 1GPa or more at a high temperature of 260 ℃, and a patterned resin film can be easily formed.
The structural formula of the photosensitive polyamic acid ester resin is shown as a formula I,
formula I
In the formula I, X is selected from at least one of groups shown in formulas IIa to IIf;
formula IIa
Formula IIb
Formula IIc
Formula IId
Formula IIe
Formula II f
Y 1 At least one selected from the group consisting of the groups represented by the formulas IIIa to IIIc;
formula IIIa
Formula IIIb
Formula IIIc
In the formula IIIb, Z 1 At least one selected from the group consisting of groups represented by formulas IVa to IVb;
formula IVa
Formula IVb
In the formula IIIc, Z 2 At least one selected from the group consisting of the groups represented by formula Va-vb;
formula Va
Formula vb
Y 2 At least one selected from the group consisting of groups represented by formulae VIa to VIm;
formula VIa
Formula VIb
Formula VI c
Formula VI d
Formula VI e
Formula VI f
Formula VI g
Formula VIh
Formula VI i
Formula VIj
Formula VI k
Formula VI l
Formula VI m
R 1 And R 2 Each independently selected from at least one of hydrogen, C1-C20 alkyl, C3-C20 cycloalkyl and monovalent organic group with carbon-carbon unsaturated double bond;
m and n represent polymerization degrees, the value range of m ranges from 30 to 150, and the value range of n ranges from 0 to 150 but is not 0.
According to the invention, the photosensitive polyamic acid ester resin is prepared from fluorine-containing aromatic dianhydride, benzoxazole group-containing aromatic diamine, aromatic diamine and an esterifying reagent, and the polyimide film is obtained by thermal imidization, so that the polyimide film not only has the characteristics of high temperature resistance, high modulus, low thermal expansion and the like, but also has the characteristics of low dielectric constant (Dk is less than or equal to 2.5) and low dielectric loss (Df is less than or equal to 0.006), and meanwhile, due to the introduction of fluorine atoms, the transparency of the polyimide film is improved, so that the film has excellent i-ray transmittance and improved resolution; the introduction of the benzoxazole group enables the Tg of PI to be larger than 300 ℃, the modulus of more than 1GPa can be maintained at the high temperature of 260 ℃, and the molten tin can not flow when the electronic component is subjected to reflow soldering; a patterned resin film (a patterned resin film) can be easily formed by introducing a photosensitive group into a polyimide precursor by an esterification agent; by curing such a pattern resin film by heating, a pattern cured film (a cured film formed by patterning) can be easily formed; meanwhile, through the esterification reagent, the polyamic acid is changed into polyesteramide, so that the self-degradation of the polyimide precursor is prevented, and the stability and the practicability of the polyimide are improved.
In the polyamic acid ester resin represented by the above formula I, preferably, R 1 And R 2 Each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, t-butyl, n-hexyl, cyclohexyl, ethyl acrylate, ethyl methacrylate, propyl acrylate and methyl propylAny one of 2-hydroxy n-propyl enoate.
As an example, in the polyamic acid ester resin of formula I, X is a group of formula IIa, Y 1 Is a group of the formula IIIa, Y 2 Is a group of the formula VIa, R 1 Is an ethyl methacrylate group, R 2 Is an ethyl methacrylate group.
The invention provides a preparation method of the polyamic acid ester resin, which comprises the following steps:
(1) Reacting fluorine-containing aromatic dianhydride with an esterification reagent to generate fluorine-containing aromatic diester diacid;
the fluorine-containing aromatic dianhydride is one compound or a mixture of two or more compounds of 6FDA, 6FXDA, 3FCDA, 6FBPADA, 6FPMDA and 3 FDAPA;
the esterifying reagent is R 1 OH and R 2 OH, wherein R 1 、R 2 The definition of (A) is the same as that of formula I;
(2) Reacting the fluorine-containing aromatic diester diacid generated in the step (1) with an acyl chlorination reagent to form corresponding diester diacid chloride;
(3) Sequentially adding aromatic diamine containing benzoxazole and aromatic diamine containing non-benzoxazole into an organic solvent, and stirring to dissolve the aromatic diamine and the non-benzoxazole to form a homogeneous mixed diamine solution;
<xnotran> 3,3' - ( [1,2-d;5,4-d ' ] -2,6- ) - ,4,4' - ( [1,2-d;5,4-d ' ] -2,6- ) - ,5,5 ' - ( [1,2-d;5,4-d ' ] -2,6- ) - (2- ), 4,4' - ( [1,2-d;5,4-d ' ] -2,6- ) - (3- ), 3,3' - ( [1,2-d;5,4-d ' ] -2,6- ) - (2- ), 3,3' - ([ 5,5' - [ d ] ] -2,2' - ) - ,4,4' - ([ 5,5' - [ d ] ] -2,2' - ) - , (2- (4- -2- ) [ d ] -5- ) - ,5,5 ' - ([ 5,5' - [ d ] ] -2,2' - ) - (2- ), (2- (3- ) [ d ] -5- ) , (2- (3- -2- ) [ d ] -5- ) </xnotran> One or more of methanone, 3'- ([ 6,6' -biphenylo [ d ] oxazole ] -2,2 '-diyl) -bis (2-methylaniline), 3' - ([ 6,6 '-biphenylo [ d ] oxazole ] -2,2' -diyl) -bis (4-methylaniline), 5'- ([ 6,6' -biphenylo [ d ] oxazole ] -2,2 '-diyl) -bis (3-methylaniline), 5' - ([ 6,6 '-biphenylo [ d ] oxazole ] -2,2' -diyl) -bis (2-methylaniline), bis (2- (3-aminophenyl) benzo [ d ] oxazol-6-yl) methanone, bis (2- (3-amino-2-benzyl) benzo [ d ] oxazol-6-yl) methanone, bis (2- (5-amino-2-benzyl) benzo [ d ] oxazol-6-yl) methanone and bis (2- (3-amino-5-benzyl) benzo [ d ] oxazol-6-yl) methanone in any ratio;
the non-benzoxazole-containing aromatic diamine is one or a mixture of more than one of m-phenylenediamine, p-phenylenediamine, 4' -diaminodiphenyl ether, 1, 3-bis (4-aminobenzyl) benzene, 1, 4-bis (4-amino-4, 4' -diisopropylbenzene) benzene, 1, 3-bis (4-amino-4, 4' -diisopropylbenzene) benzene, 4' -bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl ] ether, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, bis (3-amino-4-hydroxyphenyl) ether, 4' -bis (4-aminophenoxy) diphenyl ether, 2' -bis [4- (4-aminophenoxy phenyl) ] propane, 3' -diaminodiphenyl sulfone, 3, 4' -diaminodiphenyl sulfone and 4,4' -diaminodiphenyl sulfone in any proportion;
(4) Mixing the diester diacid chloride in the step (2) with the mixed diamine solution and the molecular weight regulator in the step (3) to carry out polycondensation reaction to generate a polyamic acid ester resin solution;
(5) Mixing the polyamic acid ester resin solution with a poor solvent to precipitate solid resin; and cleaning and drying the solid resin to obtain the photosensitive polyamic acid ester resin.
In the preparation method, in the step (1), the structural formulas of 6FDA, 6FXDA, 3FCDA, 6FBPADA, 6FPMDA and 3FDAPA are respectively as follows:
the esterification reagent is preferably an unsaturated double bond-containing alcohol compound, including but not limited to: one of 2-hydroxyethyl methacrylate (HEMA), 2-acryloyloxyethanol, 1-acryloyloxy-3-propanol, 2-acrylamidoethanol, hydroxymethylvinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-tert-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropylacrylate, 2-methacryloyloxyethanol, 1-methacryloyloxy-3-propanol, 2-methacrylamidoglycol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate and 2-hydroxy-3-cyclohexyloxypropyl methacrylate, and a mixture of a plurality thereof mixed in any proportion;
the esterification reaction is carried out under the action of an alkaline catalyst;
the basic catalyst is pyridine or triethylamine;
the esterification reaction is carried out in an organic solvent, which may be at least one of N-methylpyrrolidone (NMP), N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), and Dimethylsulfoxide (DMSO);
the molar ratio of the fluorinated aromatic dianhydride to the esterification reagent can be 1;
the temperature of the esterification reaction can be 20 to 150 ℃, such as 25 ℃; the esterification reaction time can be 0.5 to 96 hours, such as 6 hours;
the esterification reaction is carried out under stirring conditions.
In the above production method, in the step (2), the molar ratio of the fluorine-containing aromatic diester diacid to the acid chloride is preferably 1:1.5 to 3.
The acylchlorinating agent may be SOCl 2 、PCl 3 、PCl 5 Oxalyl chloride or COCl 2 ；
The reaction temperature may be-30 to 50 deg.C, preferably-20 to 25 deg.C, and the reaction time may be 1 to 48 hours, such as 4 hours.
In the above preparation method, in the step (3), the molar ratio of the benzoxazole-containing aromatic diamine to the non-benzoxazole-containing aromatic diamine may be 1: (0.1 to 0.5);
in the above preparation method, in the step (4), the molar ratio of the diester diacid chloride to the mixed diamine may be 1: (0.8-1.2);
the polycondensation reaction temperature can be-30-10 ℃; the stirring reaction time is 0.5 to 96 hours, preferably 1 to 24 hours;
the polycondensation reaction comprises the following steps: and (3) dripping the organic solution of diester diacid chloride into the mixed diamine solution, reacting for 5 to 15h after dripping is finished, adding the molecular weight regulator, and continuously reacting for 0.5 to 2h to form the polyamic acid ester resin solution.
Preferably, the molecular weight regulator is one compound or a mixture of two or more compounds selected from phthalic anhydride, hydrogenated phthalic anhydride, 4-phenylacetylene phthalic anhydride, hydrogenated 4-methylbenzene anhydride, 3-chlorobenzene anhydride, 3-bromobenzene anhydride, 4-chlorobenzene anhydride, 4-bromobenzene anhydride, perchlorobenzene anhydride, perbromobenzene anhydride, 3, 4-dichlorobenzoic anhydride, 3, 4-dibromobenzoic anhydride, aniline, 4-phenylethynylaniline and 3-phenylethynylaniline;
the organic solvent in the mixed diamine solution can be at least one of N-methylpyrrolidone (NMP), N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO);
the mass percentage concentration of the aromatic diamine containing benzoxazole and the aromatic diamine not containing benzoxazole in the mixed diamine solution can be both 5-35%, for example, the mass percentage concentration of the aromatic diamine containing benzoxazole is 13%;
preferably, the molecular weight regulator is used in such an amount that the molar ratio of acid anhydride groups to amino groups in the final reaction solution is 1:1.
in the above preparation method, in the step (5), the poor solvent may be deionized water, methanol, ethanol, hexane, butyl cellosolve, toluene, or the like, preferably deionized water, methanol, or ethanol;
the amount of the poor solvent is preferably 3 to 20 times by mass relative to the total amount of the polymer solution;
in the cleaning step, the poor solvent used for the precipitation is used for cleaning, and the amount of the poor solvent used for cleaning is preferably 1 to 6 times by mass relative to the polymer. The more times the polymer is washed, the less impurity the polymer can be obtained. The number of washing is preferably 2 to 6.
The drying is preferably carried out at 20 to 70 ℃ under vacuum, thereby obtaining a polyesteramide solid resin.
The invention further provides a resin composition which is prepared from the following components in parts by mass: 100 portions of the polyamide acid ester resin, 1 to 10 portions of the photoinitiator, 0.01 to 30 portions of the photosensitizer, 0.01 to 30 portions of the polymerization inhibitor, 0.01 to 30 portions of the crosslinking assistant and 100 to 1000 portions of the organic solvent.
By way of example, the resin composition is made from the following components in parts by mass: 100 parts of the polyamide acid ester resin, 1.5 parts of a photoinitiator, 0.25 part of a photosensitizer, 0.075 part of a polymerization inhibitor, 10 parts of a crosslinking assistant and 200 parts of an organic solvent.
In the above resin composition, the photoinitiator may be at least one of an oxime ester compound (e.g., 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1, 2-butanedione-2- (O-methoxycarbonyl) oxime, and 1, 3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime), benzophenone, N '-tetramethyl-4, 4' -diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butanone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinyl-1-propanone, alkylanthraquinone, benzoin alkyl ether, benzoin, alkylbenzoin, and benzil dimethyl ketal, preferably an oxime ester compound and benzophenone; the oxime ester compound is preferably 2-propanedione-2- (O-methoxycarbonyl) oxime.
The sensitizer may be at least one of Michler's ketone, 2, 5-bis (4 ' -diethylaminobenzylidene) cyclopentane, 4' -bis (diethylamino) benzophenone, 2, 6-bis (4 ' -diethylaminobenzylidene) cyclohexanone, 4' -bis (dimethylamino) chalcone, 4' -bis (diethylamino) chalcone, p-dimethylaminocinnamoyliminoindanone, 2, 6-bis (4 ' -diethylaminobenzylidene) -4-methylcyclohexanone, p-dimethylaminobenzylindanone, 1, 3-bis (4 ' -dimethylaminobenzylidene) acetone, 1, 3-bis (4 ' -diethylaminobenzylidene) acetone, 2- (p-dimethylaminobhenylbiphenylene) -benzothiazole, 2- (p-dimethylaminobenylvinylene) benzothiazole, and 2- (p-dimethylaminobhenylvinylene) isonaphthothiazole;
the polymerization inhibitor may be at least one of hydroquinone, 2, 6-di-t-butyl-p-methylphenol, 4-methoxyphenol, p-t-butylcatechol, phenothiazine, N-phenylnaphthylamine, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, N-nitrosodiphenylamine, 2-nitroso-1-naphthol, and 2-nitroso-5- (N-ethyl-sulfopropylamino) phenol;
the crosslinking assistant can be at least one of 2-hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, glycidyl methacrylate, ethylene glycol diether acrylate and polyethylene glycol methacrylate;
the organic solvent may be at least one of N-methylpyrrolidone (NMP), N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), and Dimethylsulfoxide (DMSO).
In the present invention, the preparation method of the resin composition comprises the steps of: and mixing the photosensitive polyamic acid ester resin, the photoinitiator, the photosensitizer, the polymerization inhibitor, the crosslinking assistant and the organic solvent, and stirring until a uniform solution is formed to obtain the resin composition.
Preferably, the preparation process is completed in a thousand-grade ultra-clean room provided with a yellow light source;
preferably, the order of addition of the raw materials is as follows: sequentially adding the photosensitive polyamic acid ester resin, the photoinitiator, the photosensitizer, the polymerization inhibitor and the crosslinking assistant into the organic solvent;
preferably, the preparation is carried out at room temperature, for example at 15 to 30 ℃ and then at 25 ℃.
Preferably, the stirring time is 8-72 h;
in the invention, the solid content of the resin composition is 10-30 wt%, and the apparent viscosity at 25 ℃ is 2000-3 multiplied by 10 5 Cp。
In the invention, the introduction of fluorine atoms reduces the electronic polarization effect, and the free volume fraction of the system is increased along with the increase of the fluorine content, so that the dielectric constant is linearly reduced along with the increase of the fluorine content; the benzoxazole group has the characteristics of long rigidity, linearity and coplanar structure, and when the benzoxazole group is introduced into a polyimide molecular chain, the proportion of polar imide rings can be reduced, the interaction force among the molecular chains is weakened, the in-plane orientation of the molecular chain is kept, meanwhile, the molecular chain is regularly stacked to form a periodic layered crystal structure, the crystallinity is higher, and the benzoxazole group and the molecular chain jointly endow the film with lower thermal expansion, higher mechanical strength, higher glass transition temperature and modulus. Hetero atoms in the benzoxazole group and metal form a metal-azole complex with good stability, so that the adhesion performance between the polyimide film and the metal is improved. The addition of the photoinitiator, the photosensitizer, the polymerization inhibitor and the crosslinking assistant can improve the light sensitivity of the low-dielectric photosensitive polyamic acid ester resin composition containing benzoxazole groups, improve the storage stability of the low-dielectric photosensitive polyamic acid ester resin composition, and further improve the mechanical property of the final polyimide film and the bonding force between the polyimide film and a substrate.
In the present invention, the method for forming a polyimide layer film from the resin composition comprises the steps of:
1) Coating: coating the resin composition on a surface of a substrate;
2) Pre-baking: evaporating 60 to 90% of the solvent from the resin composition to form a resin coating film;
3) Exposure: covering a photomask plate on the resin coating film, and exposing by adopting ultraviolet exposure equipment;
4) And (3) developing: dissolving and removing unexposed parts by adopting a developer, and then cleaning by using a rinsing liquid to obtain a required incompletely-cured resin pattern;
5) And (3) complete curing: and heating and curing the polyesteramide resin forming the resin pattern to convert the resin pattern into a polyimide layer film.
The coating in the step 1) can adopt a spin coating method, a dip coating method, a spraying method or a screen printing method.
The above method, step 2), forms the resin coating film by baking in a hot plate or oven at 80-130 ℃ for 1-60 min.
In the method, the developer and the rinsing liquid can adopt the auxiliary agents which are conventionally used in the prior art. Among them, the developer is preferably a good solvent of the negative photosensitive resin composition or a combination of a good solvent and a poor solvent. The good solvent is preferably N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N-dimethylacetamide, cyclopentanone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone or gamma-butyrolactone; the poor solvent is preferably methanol, ethanol, isopropanol, ethyl lactate, ethyl acetate, butyl acetate, tetrahydrofuran, dioxane, propylene glycol monomethyl ether or propylene glycol methyl ether acetate; the rinsing liquid is preferably at least one of isopropanol, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, ethyl lactate, cyclopentanone, and cyclohexanone.
In the above method, after the resin composition is formed into a cured film, the resin composition layer forming step, the exposure step, and the development treatment step are again performed in this order. In particular, the resin composition layer forming step, the exposure step, and the development treatment step are preferably further performed 2 to 5 times (i.e., 3 to 6 times in total) in this order. By laminating the cured films in this manner, a laminate can be obtained. In the present invention, it is particularly preferable that after the cured film is provided and developed, a new metal wiring is formed by an electroplating technique after a portion removed by the developing solution to connect the original aluminum pad or gold pad, thereby completing a Redistribution Layer (RDL).
The invention also provides the application of the resin composition as a photoresist in the following A1) or A2):
a1 Preparing an insulating layer film, a dielectric layer film or a stress buffer protective layer film in the microelectronic packaging industry;
a2 An interlayer dielectric or insulating membrane for making a multilayer metal wiring interconnect structure.
Specifically, the cured pattern film can be used as a surface protective film for electronic components, an interlayer insulating film for multilayer wiring boards, and the like. Among them, the method can be particularly suitable for a Redistribution Layer (RDL) process in a package.
An electronic part comprising a pattern cured film made of the resin composition is also within the scope of the present invention. Examples of the electronic component include a semiconductor device, a multilayer wiring board, and various electronic devices.
The invention has the following beneficial effects:
the polyimide film obtained by thermal imidization of the photosensitive polyamic acid ester resin not only has the characteristics of high temperature resistance, high modulus, low thermal expansion and the like, but also has the characteristics of low dielectric constant (Dk is less than or equal to 2.5) and low dielectric loss (Df is less than or equal to 0.006), and simultaneously, the transparency of the polyimide film is improved due to the introduction of fluorine atoms, so that the film has excellent i-ray transmittance and the resolution is improved; the introduction of the benzoxazole group enables the Tg of PI to be larger than 300 ℃, the modulus of more than 1GPa can be maintained at the high temperature of 260 ℃, and the molten tin can not flow when the electronic component is subjected to reflow soldering; a patterned resin film can be easily formed by introducing a photosensitive group into a polyimide precursor by an esterification reagent; by heating and curing the pattern resin film, the pattern cured film can be easily formed; meanwhile, through the esterification reagent, the polyamic acid is changed into polyesteramide, so that the self-degradation of the polyimide precursor is prevented, and the stability and the practicability of the polyimide are improved.
As one application of the present invention, a manufacturing process of an electronic component will be described with reference to the drawings. Fig. 1 is a schematic sectional view illustrating a manufacturing process of an electronic component having a wiring structure.
The resin composition solution is spin-coated on a semiconductor substrate 1 such as a Si substrate by a spin coating method, and exposure and development are performed to obtain a polyimide film, a first polyimide layer 2 is formed, a conductor layer 3 is formed in an exposed window, a second polyimide layer 4 serving as an interlayer insulating film is formed on the first polyimide layer 2 by a spin coating method or the like, after exposure and development, a new Metal wiring 5 is formed in the window exposed on the second polyimide layer 4 by a plating technique, a third polyimide layer 6 serving as an interlayer insulating film is formed on the Metal wiring 5 by a spin coating method or the like, after exposure and development, a plating resist layer is formed in accordance with the window in the window exposed on the third polyimide layer 6 by a known method, a Metal layer 7 called UBM (Under Bump Metal) is deposited on the exposed Metal film portion by plating, and further, an external connection terminal 8 called a Bump is formed on the surface of the Metal layer 7, thereby obtaining the electronic component shown in fig. 1.
The electronic component has a pattern cured film of the resin composition solution containing the photosensitive polyamic acid ester resin. Examples of the electronic component include a semiconductor device, a multilayer wiring board, and various electronic devices. Specifically, the cured pattern film can be used as a surface protective film for electronic components, an interlayer insulating film for multilayer wiring boards, and the like. Among them, the method can be particularly suitable for a Redistribution Layer (RDL) process in a package.
Drawings
Fig. 1 is a schematic diagram of an electronic component in at least one embodiment of the invention.
The respective labels in fig. 1 are as follows: 1-a semiconductor substrate; 2-a first polyimide layer; 3-a conductor layer; 4-a second polyimide layer; 5-a metal line; 6-a third polyimide layer; 7-a metal layer; 8-external connection terminals.
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, which are given for the purpose of illustration only and are not intended to limit the scope of the invention. The examples provided below serve as a guide for further modifications by a person skilled in the art and do not constitute a limitation of the invention in any way.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are commercially available unless otherwise specified.
The glass transition temperature of the polyimide film was measured using dynamic thermo-mechanical analysis (DMA). Dynamic thermomechanical analyzer: type Q800 from TA usa.
Example 1
1. Preparation of photosensitive polyamic acid ester resin
(1) 89.12g of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6 FDA), 52.24g of 2-hydroxyethyl methacrylate (HEMA), 28.44g of pyridine and 232g of N-methylpyrrolidone (NMP) were sequentially added to a 1L three-necked round bottom flask equipped with electric stirring and nitrogen inlet and outlet, and stirred at room temperature for 6 hours to produce the corresponding 6 FDA-diacid dimethacrylate. 47.60g of SOCl were then slowly added dropwise 2 Reacting for 2h at 0-10 ℃ and reacting for 4h at room temperature to generate corresponding mixed diacid chloride dimethacrylate.
(2) 47.92 g of 4,4'- (benzo [1,2-d;5,4-d' ] dioxazole-2, 6-diyl) -diphenylamine (BABO), 6.51 g of p-phenylenediamine and 306g of NMP are sequentially added to a 1L three-neck round-bottom flask equipped with electric stirring and a nitrogen inlet and outlet, and stirred to be dissolved to form a homogeneous transparent mixed diamine solution; cooling the mixed diamine solution to below 10 ℃ by adopting an ice bath, and dropwise adding the prepared mixed diacid chloride dimethacrylate into the mixed diamine solution for 1h; then, reacting for 10 hours at room temperature; then adding 2.98g of phthalic anhydride, and continuing stirring for 1h; and pouring the reaction solution into 5L of deionized water, separating out a solid, filtering, and drying in vacuum to obtain the polyamic acid ester resin.
2. Preparation of Polyamic acid ester resin composition solution
40g of the above polyamic acid ester resin, 0.6g of 2-propanedione-2- (O-methoxycarbonyl) oxime, 0.10 g of 2, 6-bis (4' -diethylaminobenzylidene) cyclohexanone, 0.03g of 2, 6-di-t-butyl-p-methylphenol and 4.0g of 2-hydroxyethyl methacrylate were sequentially added to 80g of NMP in a thousand-stage super clean room equipped with a yellow light lamp, and stirred at room temperature for 3 hours to form a homogeneous, negative photosensitive polyamic acid ester resin composition solution.
3. Preparation of polyimide film
Spin-coating the solution of the negative photosensitive polyamic acid ester resin composition on the surface of a 6-inch wafer by using a spin coater; 110. baking at deg.C for 4min, placing a mask on the surface, and exposing with ultraviolet lamp (i and g rays) for 30s; developing with cyclopentanone, washing with ethyl acetate, and heating by program in nitrogen oven (60) o C/1h，80 o C/1h，120 o C/1h，170 o C/1h，250 o C/1h，300 o C/1h，350 o C/1 h) to obtain a polyimide film photoetching pattern with the pattern resolution of 10 mu m. The high-temperature modulus (260 ℃) of the obtained polyimide film is 1.2GPa, the dielectric constant is 2.4, the dielectric loss is 0.0035, the water absorption rate is 0.39 percent, and the glass transition temperature is 325 ℃.
Example 2
1. Preparation of photosensitive polyamic acid ester resin
54.75g of 4,4'- (benzo [1,2-d;5,4-d' ] dioxazole-2, 6-diyl) -diphenylamine (BABO), 4.32g of p-phenylenediamine and 306g of NMP are sequentially added into a 1L three-neck round-bottom flask which is provided with an electric stirring device and a nitrogen inlet and outlet, and stirred to be dissolved to form a homogeneous transparent mixed diamine solution; cooling the mixed diamine solution to below 10 ℃ by adopting an ice bath, and dropwise adding the mixed diacid-chloride dimethacrylate prepared in the example 1 into the mixed diamine solution for 1h; then, reacting for 10 hours at room temperature; then adding 2.98g of phthalic anhydride, and continuing stirring for 1h; and pouring the reaction solution into 5L of deionized water, separating out a solid, filtering, and drying in vacuum to obtain the polyamic acid ester resin.
2. Preparation of Polyamic acid ester resin composition solution
40g of the above polyamic acid ester resin, 0.6g of 2-propanedione-2- (O-methoxycarbonyl) oxime, 0.10 g of 2, 6-bis (4' -diethylaminobenzylidene) cyclohexanone, 0.03g of 2, 6-di-t-butyl-p-methylphenol and 4.0g of 2-hydroxyethyl methacrylate were successively added to 80g of NMP in a thousand stages of a super clean room equipped with a yellow light lamp, and stirred at room temperature for 3 hours to form a homogeneous, negative-working polyamic acid ester resin composition solution.
3. Preparation of polyimide film
Spin-coating the solution of the negative photosensitive polyamic acid ester resin composition on the surface of a 6-inch wafer by using a spin coater; baking at 110 deg.C for 4min, placing mask on the surface, and exposing with ultraviolet lamp (i and g lines) for 30s; developing with cyclopentanone, washing with ethyl acetate, heating in nitrogen oven at 60 deg.C o C/1h，80 o C/1h，120 o C/1h，170 o C/1h，250 o C/1h，300 o C/1h，350 o C/1 h) to obtain a polyimide film photoetching pattern with the pattern resolution of 8 mu m. The high-temperature modulus (260 ℃) of the obtained polyimide film is 1.4Gpa, the dielectric constant is 2.2, the dielectric loss is 0.0031, the water absorption rate is 0.30%, and the glass transition temperature is 336 ℃.
Example 3
1. Preparation of photosensitive polyamic acid ester resin
61.56g of 4,4'- (benzo [1,2-d;5,4-d' ] dioxazole-2, 6-diyl) -diphenylamine (BABO), 2.16g of p-phenylenediamine and 306g of NMP are sequentially added into a 1L three-neck round-bottom flask provided with an electric stirring and a nitrogen inlet and outlet, and stirred to be dissolved to form a homogeneous transparent mixed diamine solution; cooling the mixed diamine solution to below 10 ℃ by adopting an ice bath, and dropwise adding the mixed diacid chloride dimethacrylate prepared in the example 1 into the mixed diamine solution for 1h; then, reacting for 10 hours at room temperature; then adding 2.98g of phthalic anhydride, and continuing stirring for 1h; and pouring the reaction solution into 5L of deionized water, separating out a solid, filtering, and drying in vacuum to obtain the polyamic acid ester resin.
2. Preparation of Polyamic acid ester resin composition solution
40g of the above polyamic acid ester resin, 0.6g of 2-propanedione-2- (O-methoxycarbonyl) oxime, 0.10 g of 2, 6-bis (4' -diethylaminobenzylidene) cyclohexanone, 0.03g of 2, 6-di-t-butyl-p-methylphenol and 4.0g of 2-hydroxyethyl methacrylate were successively added to 80g of NMP in a thousand stages of a super clean room equipped with a yellow light lamp, and stirred at room temperature for 3 hours to form a homogeneous, negative-working polyamic acid ester resin composition solution.
3. Preparation of polyimide film
Spin-coating the solution of the negative photosensitive polyamic acid ester resin composition on the surface of a 6-inch wafer by using a spin coater; baking at 110 deg.C for 4min, placing a mask on the surface, and exposing with ultraviolet lamp (i and g lines) for 30s; developing with cyclopentanone, washing with ethyl acetate, heating in nitrogen oven at 60 deg.C o C/1h，80 o C/1h，120 o C/1h，170 o C/1h，250 o C/1h，300 o C/1h，350 o C/1 h) to obtain a polyimide film photoetching pattern with the pattern resolution of 8 mu m. The polyimide film obtained had a high-temperature modulus (260 ℃) of 1.6GPa, a dielectric constant of 2.0, a dielectric loss of 0.0025, a water absorption of 0.23% and a glass transition temperature of 351 ℃.
Example 4
1. Preparation of photosensitive polyamic acid ester resin
(1) 75.24g of 4,4' - ([ 5,5' -biphenyl [ d ] oxazole ] -2,2' -diyl) -diphenylamine (HAAB), 2.16g of p-phenylenediamine and 306g of NMP are sequentially added into a 1L three-neck round-bottom flask with an electric stirring function and a nitrogen inlet and outlet, and are stirred to be dissolved to form a homogeneous transparent mixed diamine solution; cooling the mixed diamine solution to below 10 ℃ by adopting an ice bath, and dropwise adding the mixed diacid-chloride dimethacrylate prepared in the example 1 into the mixed diamine solution for 1h; then, reacting for 10 hours at room temperature; then adding 2.98g of phthalic anhydride, and continuing stirring for 1h; and pouring the reaction solution into 5L of deionized water, separating out a solid, filtering, and drying in vacuum to obtain the polyamic acid ester resin.
2. Preparation of Polyamic acid ester resin composition solution
40g of the above polyamic acid ester resin, 0.6g of 2-propanedione-2- (O-methoxycarbonyl) oxime, 0.10 g of 2, 6-bis (4' -diethylaminobenzylidene) cyclohexanone, 0.03g of 2, 6-di-t-butyl-p-methylphenol and 4.0g of 2-hydroxyethyl methacrylate were successively added to 80g of NMP in a thousand stages of a super clean room equipped with a yellow light lamp, and stirred at room temperature for 3 hours to form a homogeneous, negative-working polyamic acid ester resin composition solution.
3. Preparation of polyimide film
Spin-coating the solution of the negative photosensitive polyamic acid ester resin composition on the surface of a 6-inch wafer by using a spin coater; baking at 110 deg.C for 4min, placing mask on the surface, and exposing with ultraviolet lamp (i and g lines) for 30s; developing with cyclopentanone, washing with ethyl acetate, and heating by program in nitrogen oven (60) o C/1h，80 o C/1h，120 o C/1h，170 o C/1h，250 o C/1h，300 o C/1h，350 o C/1 h) to obtain a polyimide film photoetching pattern with the pattern resolution of 8 mu m. The high-temperature modulus (260 ℃) of the obtained polyimide film is 1.5Gpa, the dielectric constant is 2.2, the dielectric loss is 0.0027, the water absorption rate is 0.26%, and the glass transition temperature is 335 ℃.
Comparative example 1
1. Preparation of Polyamic acid ester resin
(1) 62.05g of 3,3', 4' -diphenyl ether tetracarboxylic dianhydride (ODPA), 52.24g of 2-hydroxyethyl methacrylate (HEMA), 28.44g of pyridine and 232g of N-methylpyrrolidone (NMP) are sequentially added into a 1L three-neck round-bottom flask with electric stirring and nitrogen inlet and outlet, and the mixture is stirred at room temperature for 6 hours to generate the corresponding ODPA-diacid dimethacrylate. 47.60g of SOCl were then slowly added dropwise 2 Reacting for 2h at 0-10 ℃ and reacting for 4h at room temperature to generate corresponding mixed diacid chloride dimethacrylate.
(2) 61.56g of 4,4'- (benzo [1,2-d;5,4-d' ] dioxazole-2, 6-diyl) -diphenylamine (BABO), 2.16g of p-phenylenediamine and 306g of NMP are sequentially added into a 1L three-neck round-bottom flask which is provided with an electric stirring device and a nitrogen inlet and outlet, and stirred to be dissolved to form a homogeneous transparent mixed diamine solution; cooling the mixed diamine solution to below 10 ℃ by adopting an ice bath, and dropwise adding the prepared mixed diacid-chloride dimethacrylate into the mixed diamine solution for 1h; then, reacting for 10 hours at room temperature; then adding 2.98g of phthalic anhydride, and continuing stirring for 1h; and pouring the reaction solution into 5L of deionized water, separating out a solid, filtering, and drying in vacuum to obtain the polyamic acid ester resin.
2. Preparation of Polyamic acid ester resin composition solution
40g of the above polyamic acid ester resin, 0.6g of 2-propanedione-2- (O-methoxycarbonyl) oxime, 0.10 g of 2, 6-bis (4' -diethylaminobenzylidene) cyclohexanone, 0.03g of 2, 6-di-t-butyl-p-methylphenol and 4.0g of 2-hydroxyethyl methacrylate were successively added to 80g of NMP in a thousand-stage super clean room equipped with a yellow lamp, and stirred at room temperature for 3 hours to form a homogeneous negative photosensitive polyamic acid ester resin composition solution.
3. Preparation of polyimide film
Spin-coating the solution of the negative photosensitive polyamic acid ester resin composition on the surface of a 6-inch wafer by using a spin coater; baking at 110 deg.C for 4min, placing a mask on the surface, and exposing with ultraviolet lamp (i and g lines) for 30s; developing with cyclopentanone, washing with ethyl acetate, and heating by program in nitrogen oven (60) o C/1h，80 o C/1h，120 o C/1h，170 o C/1h，250 o C/1h，300 o C/1h，350 o C/1 h) to obtain a polyimide film photoetching pattern with the pattern resolution of 15 mu m. The polyimide film obtained had a high-temperature modulus (260 ℃ C.) of 1.4GPa, a dielectric constant of 3.5, a dielectric loss of 0.0046, a water absorption of 0.25%, and a glass transition temperature of 343 ℃.
Comparative example 2
1. Preparation of photosensitive Polyamic acid ester resin
(1) 89.12g of fluorinated aromatic dianhydride (6 FDA), 52.24g of 2-hydroxyethyl methacrylate (HEMA), 28.44g of pyridine and 232g of N-methylpyrrolidone (NMP) are sequentially added into a 1L three-neck round-bottom flask with an electric stirring function and a nitrogen inlet and outlet, and the mixture is stirred at room temperature for 6 hours to generate the corresponding 6 FDA-diacid dimethacrylate. Then 47.60g of SOCl were slowly added dropwise 2 Reacting at 0-10 ℃ for 2h and at room temperature for 4h to generate the corresponding mixed diacid chloride dimethacrylate.
(2) 36.06g of 4,4' -diaminodiphenyl ether (ODA), 2.16g of p-phenylenediamine and 306g of NMP are sequentially added into a 1L three-neck round-bottom flask with an electric stirrer and a nitrogen inlet and outlet, and stirred to be dissolved to form a homogeneous transparent mixed diamine solution; cooling the mixed diamine solution to below 10 ℃ by adopting an ice bath, and dropwise adding the prepared mixed diacid chloride dimethacrylate into the mixed diamine solution for 1h; then, reacting for 10 hours at room temperature; then adding 2.98g of phthalic anhydride, and continuing stirring for 1h; and pouring the reaction solution into 5L of deionized water, separating out a solid, filtering, and drying in vacuum to obtain the polyamic acid ester resin.
2. Preparation of Polyamic acid ester resin composition solution
40g of the above polyamic acid ester resin, 0.6g of 2-propanedione-2- (O-methoxycarbonyl) oxime, 0.10 g of 2, 6-bis (4' -diethylaminobenzylidene) cyclohexanone, 0.03g of 2, 6-di-t-butyl-p-methylphenol and 4.0g of 2-hydroxyethyl methacrylate were successively added to 80g of NMP in a thousand stages of a super clean room equipped with a yellow light lamp, and stirred at room temperature for 3 hours to form a homogeneous, negative-working polyamic acid ester resin composition solution.
3. Preparation of polyimide film
Spin-coating the solution of the negative photosensitive polyamic acid ester resin composition on the surface of a 6-inch wafer by using a spin coater; baking at 110 deg.C for 4min, placing mask on the surface, and exposing with ultraviolet lamp (i and g lines) for 30s; developing with cyclopentanone, washing with ethyl acetate, and heating by program in nitrogen oven (60) o C/1h，80 o C/1h，120 o C/1h，170 o C/1h，250 o C/1h，300 o C/1h，350 o C/1 h) to obtain a polyimide film photoetching pattern with the pattern resolution of 10 mu m. The high-temperature modulus (260 ℃) of the obtained polyimide film is 0.7GPa, the dielectric constant is 2.8, the dielectric loss is 0.0031, the water absorption rate is 0.46 percent, and the glass transition temperature is 310 ℃.
TABLE 1 Main Properties of polyimide film containing benzoxazole group
As can be seen from examples 1 to 4, comparative examples 1 and 2, and table 1, as the proportion of the benzoxazole group-containing aromatic diamine in the resin increases, the glass transition temperature and the high-temperature modulus at 260 ℃ of the resin thin film gradually increase. A resin film containing only a fluorine aromatic dianhydride and an aromatic diamine has a low dielectric constant, but has a high-temperature modulus at 260 ℃ of less than 1GPa; the resin film which does not contain fluorine aromatic dianhydride, contains benzoxazole group aromatic diamine and other aromatic diamine has a high-temperature modulus at 260 ℃ of more than 1, but has a dielectric constant of more than 3; the high-temperature modulus at 260 ℃ of the resin film consisting of only the fluorine-containing aromatic dianhydride, the aromatic diamine containing the benzoxazole group and other aromatic diamines is more than 1, and the dielectric constant is lower than 2.5.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention will be covered within the scope of the present invention.
Claims (10)
1. A photosensitive polyamic acid ester resin represented by the formula I,
formula I
In the formula I, X is selected from at least one of groups shown in formulas IIa to IIf;
formula IIa
Formula IIb
Formula IIc
Formula IId
Formula IIe
Formula II f
Y 1 At least one selected from the group consisting of the groups represented by the formulas IIIa to IIIc;
formula IIIa
Formula IIIb
Formula IIIc
In the formula IIIb, Z 1 At least one selected from the group consisting of groups represented by formulas IVa to IVb;
formula IVa
Formula IVb
In the formula IIIc, Z 2 At least one selected from the group consisting of the groups represented by formula Va-vb;
formula Va
Formula vb
Y 2 At least one selected from the group consisting of groups represented by formulas VIa to VIm;
formula VIa
Formula VIb
Formula VI c
Formula VI d
Formula VI e
Formula VI f
Formula VI g
Formula VIh
Formula VI i
Formula VIj
Formula VI k
Formula VI l
Formula VI m
R 1 And R 2 Each independently selected from at least one of hydrogen, C1-C20 alkyl, C3-C20 cycloalkyl and monovalent organic group with carbon-carbon unsaturated double bond;
m and n represent polymerization degrees, the range of m is 30 to 150, and the range of n is 0 to 150 but not 0.
2. The photosensitive polyamic acid ester resin according to claim 1, wherein: r is 1 And R 2 Each independently selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, n-hexyl, cyclohexyl, ethyl acrylate, ethyl methacrylate, propyl acrylate and 2-hydroxy-n-propyl methacrylate.
3. The method for preparing the photosensitive polyamic acid ester resin according to claim 1 or 2, comprising the steps of:
(1) Reacting fluorine-containing aromatic dianhydride with an esterification reagent to generate fluorine-containing aromatic diester diacid;
the fluorine-containing aromatic dianhydride is one compound or a mixture of two or more compounds of 6FDA, 6FXDA, 3FCDA, 6FBPADA, 6FPMDA and 3 FDAPA;
the esterifying reagent is R 1 OH and R 2 OH, wherein R 1 、R 2 The definition of (A) is the same as that of formula I;
(2) Reacting the fluorine-containing aromatic diester diacid generated in the step (1) with an acyl chlorination reagent to generate corresponding diester diacid chloride;
(3) Sequentially adding aromatic diamine containing benzoxazole and non-aromatic diamine containing benzoxazole into an organic solvent, and stirring to dissolve the aromatic diamine and the non-aromatic diamine to form a homogeneous mixed diamine solution;
<xnotran> 3,3' - ( [1,2-d;5,4-d ' ] -2,6- ) - ,4,4' - ( [1,2-d;5,4-d ' ] -2,6- ) - ,5,5 ' - ( [1,2-d;5,4-d ' ] -2,6- ) - (2- ), 4,4' - ( [1,2-d;5,4-d ' ] -2,6- ) - (3- ), 3,3' - ( [1,2-d;5,4-d ' ] -2,6- ) - (2- ), 3,3' - ([ 5,5' - [ d ] ] -2,2' - ) - ,4,4' - ([ 5,5' - [ d ] ] -2,2' - ) - , (2- (4- -2- ) [ d ] -5- ) - ,5,5 ' - ([ 5,5' - [ d ] ] -2,2' - ) - (2- ), (2- (3- ) [ d ] -5- ) , (2- (3- -2- ) [ d ] -5- ) </xnotran> Methanone, 3'- ([ 6,6' -biphenylo [ d ] oxazole ] -2,2 '-diyl) -bis (2-methylaniline), 3' - ([ 6,6 '-biphenylo [ d ] oxazole ] -2,2' -diyl) -bis (4-methylaniline), 5'- ([ 6,6' -biphenylo [ d ] oxazole ] -2,2 '-diyl) -bis (3-methylaniline), 5' - ([ 6,6 '-biphenylo [ d ] oxazole ] -2,2' -diyl) -bis (2-methylaniline), bis (2- (3-aminophenyl) benzo [ d ] oxazol-6-yl) methanone, bis (2- (3-amino-2-benzyl) benzo [ d ] oxazol-6-yl) methanone, bis (2- (5-amino-2-benzyl) benzo [ d ] oxazol-6-yl) methanone, and bis (2- (3-amino-5-benzyl) benzo [ d ] oxazol-6-yl) methanone in any proportion or in a mixture thereof;
the non-benzoxazole-containing aromatic diamine is one or a mixture of m-phenylenediamine, p-phenylenediamine, 4' -diaminodiphenyl ether, 1, 3-bis (4-aminobenzyl) benzene, 1, 4-bis (4-amino-4, 4' -diisopropylbenzene) benzene, 1, 3-bis (4-amino-4, 4' -diisopropylbenzene) benzene, 4' -bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl ] ether, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, bis (3-amino-4-hydroxyphenyl) ether, 4' -bis (4-aminophenoxy) diphenyl ether, 2' -bis [4- (4-aminophenoxy phenyl) ] propane, 3' -diaminodiphenyl sulfone, 3, 4' -diaminodiphenyl sulfone, and 4,4' -diaminodiphenyl sulfone in any ratio;
(4) Mixing the diester diacid chloride in the step (2) with the mixed diamine solution and the molecular weight regulator in the step (3) to carry out polycondensation reaction to generate a polyamic acid ester resin solution;
(5) Mixing the polyamic acid ester resin solution with a poor solvent to precipitate solid resin; and cleaning and drying the solid resin to obtain the photosensitive polyamic acid ester resin.
4. The production method according to claim 3, characterized in that: in the step (1), the molar ratio of the fluorine-containing aromatic dianhydride to the esterification reagent is 1:2;
the esterification reaction is carried out under the action of an alkaline catalyst;
the basic catalyst is pyridine or triethylamine;
the esterification reaction is carried out in an organic solvent, wherein the organic solvent is at least one of N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide and dimethyl sulfoxide;
the temperature of the esterification reaction is 20-150 ℃, and the time is 0.5-96 h;
the esterification reaction is carried out under stirring conditions.
5. The production method according to claim 3, characterized in that: in the step (2), the molar ratio of the fluorine-containing aromatic diester diacid to the acyl chlorination reagent is 1: (1.5-3);
the acyl chlorination reagent is SOCl 2 、PCl 3 、PCl 5 Oxalyl chloride or COCl 2 ；
The reaction temperature is-30-50 ℃ and the reaction time is 1-48 h.
6. The production method according to claim 3, characterized in that: in the step (3), the molar ratio of the benzoxazole-containing aromatic diamine to the non-benzoxazole-containing aromatic diamine is 1: (0.1-0.5);
in the step (4), the molar ratio of the diester diacid chloride to the mixed diamine is 1: (0.8-1.2);
the temperature of the polycondensation reaction is-30 to 10 ℃;
the polycondensation reaction comprises the following steps: dripping the organic solution of diester diacid chloride into the mixed diamine solution, reacting for 5 to 15h after the dripping is finished, adding the molecular weight regulator, and continuing to react for 0.5 to 2h to form a polyamic acid resin solution;
the molecular weight regulator is one compound or a mixture of two or more compounds of phthalic anhydride, hydrogenated phthalic anhydride, 4-phenylacetylene phthalic anhydride, hydrogenated 4-methylbenzene anhydride, 3-chlorobenzene anhydride, 3-bromobenzene anhydride, 4-chlorobenzene anhydride, 4-bromobenzene anhydride, perchlorobenzene anhydride, perbromobenzene anhydride, 3, 4-dichlorobenzene anhydride, 3, 4-dibromobenzene anhydride, aniline, 4-phenylethynyl aniline and 3-phenylethynyl aniline;
the organic solvent in the mixed diamine solution is at least one of N-methyl pyrrolidone, N-dimethylacetamide, N-dimethylformamide and dimethyl sulfoxide;
the mass percentage concentration of aromatic diamine containing benzoxazole and aromatic diamine not containing benzoxazole in the mixed diamine solution is 5-35%;
the amount of the molecular weight regulator is such that the molar ratio of the acid anhydride groups to the amino groups in the final reaction solution is 1:1.
7. a resin composition characterized by: the composition is prepared from the following components in parts by mass: 100 parts of the polyamic acid ester resin, 1-10 parts of photoinitiator, 0.01-30 parts of photosensitizer, 0.01-30 parts of polymerization inhibitor, 0.01-30 parts of crosslinking assistant and 100-1000 parts of organic solvent.
8. The resin composition according to claim 7, characterized in that: the photoinitiator is at least one of oxime ester compounds, benzophenone, N '-tetramethyl-4, 4' -diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinyl phenyl) butanone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinyl-1-acetone, alkylanthraquinone, benzoin alkyl ether, benzoin, alkyl benzoin and benzil dimethyl ketal;
the sensitizer is at least one of Michler's ketone, 2, 5-bis (4 ' -diethylaminobenzylidene) cyclopentane, 4' -bis (diethylamino) benzophenone, 2, 6-bis (4 ' -diethylaminobenzylidene) cyclohexanone, 4' -bis (dimethylamino) chalcone, 4' -bis (diethylamino) chalcone, p-dimethylaminocinnamoyliminoindanone, 2, 6-bis (4 ' -diethylaminobenzylidene) -4-methylcyclohexanone, p-dimethylaminobenzylindanone, 1, 3-bis (4 ' -dimethylaminobenzylidene) acetone, 1, 3-bis (4 ' -diethylaminobenzylidene) acetone, 2- (p-dimethylaminobhenylbiphenylene) -benzothiazole, 2- (p-dimethylaminobenylvinylene) benzothiazole, and 2- (p-dimethylaminobhenylvinylene) isonaphthothiazole;
the polymerization inhibitor is at least one of hydroquinone, 2, 6-di-tert-butyl-p-methylphenol, 4-methoxyphenol, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, N-nitrosodiphenylamine, 2-nitroso-1-naphthol, and 2-nitroso-5- (N-ethyl-sulfopropylamino) phenol;
the crosslinking assistant is at least one of 2-hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, glycidyl methacrylate, ethylene glycol monoethyl ether acrylate and polyethylene glycol methacrylate;
the organic solvent is at least one of N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide and dimethyl sulfoxide.
9. Use of the resin composition according to claim 7 or 8 as a photoresist in A1) or A2) as follows:
a1 Preparing an insulating layer film, a dielectric layer film or a stress buffer protective layer film in the microelectronic packaging industry;
a2 An interlayer dielectric or insulating membrane for making a multilayer metal wiring interconnect structure.
10. An electronic component characterized by: comprising a pattern cured film made of the resin composition according to claim 7 or 8.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116333303A (en) * | 2023-05-25 | 2023-06-27 | 明士(北京)新材料开发有限公司 | Anti-mould-pressing alkaline aqueous development photosensitive adhesive film and application thereof |
| CN116836388A (en) * | 2023-08-30 | 2023-10-03 | 明士(北京)新材料开发有限公司 | Positive photosensitive resin, resin composition, preparation method and application thereof |
| CN117384378A (en) * | 2023-10-26 | 2024-01-12 | 明士(北京)新材料开发有限公司 | Photosensitive polyamic acid ester resin, resin composition, preparation method and application thereof |
| CN117430812A (en) * | 2023-12-21 | 2024-01-23 | 明士(北京)新材料开发有限公司 | Photosensitive polyamic acid ester resin, resin composition and application |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995004305A1 (en) * | 1993-07-28 | 1995-02-09 | E.I. Du Pont De Nemours And Company | Photosensitive fluorinated poly(amic acid) aminoacrylate salt |
| US20010056174A1 (en) * | 1999-12-28 | 2001-12-27 | Koji Okada | Epoxy-modified polyimide, photosensitive composition, coverlay film, solder resist, and printed wiring board using the epoxy-modified polyimide |
| JP2005321648A (en) * | 2004-05-10 | 2005-11-17 | Toyobo Co Ltd | Negative photosensitive polyimide precursor composition |
| CN1726259A (en) * | 2002-12-13 | 2006-01-25 | 株式会社钟化 | Thermoplastic polyimide resin film, multilayer body and method for manufacturing printed wiring board composed of same |
| CN110003470A (en) * | 2019-04-29 | 2019-07-12 | 中国科学院长春应用化学研究所 | A kind of polyimide material and preparation method thereof applied to flexible display substrates |
| CN110028670A (en) * | 2019-04-11 | 2019-07-19 | 明士新材料有限公司 | Low-dielectric loss negative light-sensitive poly amic acid ester resin, resin combination, preparation method and application |
| CN110791833A (en) * | 2019-11-26 | 2020-02-14 | 中国科学院长春应用化学研究所 | Polyimide fiber and preparation method thereof |
| CN111019345A (en) * | 2019-12-17 | 2020-04-17 | 中国科学院化学研究所 | Poly (imide-benzoxazole) film and preparation method and application thereof |
-
2022
- 2022-09-09 CN CN202211098568.2A patent/CN115160569B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995004305A1 (en) * | 1993-07-28 | 1995-02-09 | E.I. Du Pont De Nemours And Company | Photosensitive fluorinated poly(amic acid) aminoacrylate salt |
| US20010056174A1 (en) * | 1999-12-28 | 2001-12-27 | Koji Okada | Epoxy-modified polyimide, photosensitive composition, coverlay film, solder resist, and printed wiring board using the epoxy-modified polyimide |
| CN1726259A (en) * | 2002-12-13 | 2006-01-25 | 株式会社钟化 | Thermoplastic polyimide resin film, multilayer body and method for manufacturing printed wiring board composed of same |
| JP2005321648A (en) * | 2004-05-10 | 2005-11-17 | Toyobo Co Ltd | Negative photosensitive polyimide precursor composition |
| CN110028670A (en) * | 2019-04-11 | 2019-07-19 | 明士新材料有限公司 | Low-dielectric loss negative light-sensitive poly amic acid ester resin, resin combination, preparation method and application |
| CN110003470A (en) * | 2019-04-29 | 2019-07-12 | 中国科学院长春应用化学研究所 | A kind of polyimide material and preparation method thereof applied to flexible display substrates |
| CN110791833A (en) * | 2019-11-26 | 2020-02-14 | 中国科学院长春应用化学研究所 | Polyimide fiber and preparation method thereof |
| CN111019345A (en) * | 2019-12-17 | 2020-04-17 | 中国科学院化学研究所 | Poly (imide-benzoxazole) film and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| DUYOUNG WEE等: "Poly(imide-benzoxazole) gate insulators with high thermal resistance for solution-processed flexible indium-zinc oxide thin-film transistors", 《JOURNAL OF MATERIALS CHEMISTRY C》 * |
| FENG GAN等: "Preparation of thermally rearranged poly(benzoxazole-co-imide) membranes containing heteroaromatic moieties for CO2/CH4 separation", 《POLYMER》 * |
| XIANGLI MENG等: "Thermal degradation kinetics of polyimide containing 2,6-benzobisoxazole units", 《POLYMER DEGRADATION AND STABILITY》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116333303A (en) * | 2023-05-25 | 2023-06-27 | 明士(北京)新材料开发有限公司 | Anti-mould-pressing alkaline aqueous development photosensitive adhesive film and application thereof |
| CN116333303B (en) * | 2023-05-25 | 2023-08-04 | 明士(北京)新材料开发有限公司 | Anti-mould-pressing alkaline aqueous development photosensitive adhesive film and application thereof |
| CN116836388A (en) * | 2023-08-30 | 2023-10-03 | 明士(北京)新材料开发有限公司 | Positive photosensitive resin, resin composition, preparation method and application thereof |
| CN116836388B (en) * | 2023-08-30 | 2023-12-15 | 明士(北京)新材料开发有限公司 | Positive photosensitive resin, resin composition, preparation method and application thereof |
| CN117384378A (en) * | 2023-10-26 | 2024-01-12 | 明士(北京)新材料开发有限公司 | Photosensitive polyamic acid ester resin, resin composition, preparation method and application thereof |
| CN117430812A (en) * | 2023-12-21 | 2024-01-23 | 明士(北京)新材料开发有限公司 | Photosensitive polyamic acid ester resin, resin composition and application |
| CN117430812B (en) * | 2023-12-21 | 2024-03-19 | 明士(北京)新材料开发有限公司 | Photosensitive polyamic acid ester resin, resin composition and application |
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