CN114805810B

CN114805810B - Photosensitive polyimide precursor resin, preparation method and photosensitive resin composition

Info

Publication number: CN114805810B
Application number: CN202210695425.3A
Authority: CN
Inventors: 公聪聪; 贾杰; 李铭新; 门秀婷
Original assignee: Bomi Technology Co ltd
Current assignee: Bomi Technology Co ltd
Priority date: 2022-03-23
Filing date: 2022-06-17
Publication date: 2023-06-02
Anticipated expiration: 2042-06-17
Also published as: CN114805810A

Abstract

The application relates to the field of functional polymer materials, and particularly discloses a photosensitive polyimide precursor resin, a preparation method and a photosensitive resin composition. The photosensitive polyimide precursor resin comprises at least one photosensitive molecular chain block, at least one fluorine-containing molecular chain block and at least one silicon-containing molecular chain block, wherein the fluorine-containing molecular chain block is embedded between the silicon-containing molecular chain block and the photosensitive molecular chain block; the preparation method comprises the following steps: preparing a photosensitive fragment; preparing fluorine-containing fragments; preparing a silicon-containing fragment; mixing the photosensitive segment, the fluorine-containing segment and the silicon-containing segment, and reacting for 3-24 h at the temperature of 10-100 ℃; and adding a blocking agent to carry out a blocking reaction. The photosensitive polyimide precursor resin can be used for preparing a photosensitive resin composition, and has the advantages of high permeability of the obtained film and high adhesion with a substrate.

Description

Photosensitive polyimide precursor resin, preparation method and photosensitive resin composition

Technical Field

The application relates to the field of functional polymer materials, in particular to photosensitive polyimide precursor resin, a preparation method and a photosensitive resin composition.

Background

Polyimide (PI) is one of the most widely used polymeric materials in the semiconductor and microelectronics industries today. The Polyimide (PI) skeleton has the rigid structure and the aromatic structure of the cyclic imide, so that the polyimide has good thermal stability, excellent mechanical property, electrical property and chemical property, and is widely applied to the fields of electronics, optics, aerospace, photoelectric devices and the like. With the light weight, high performance and multifunction of electronic products, the requirements on Polyimide (PI) are also increasing.

The adhesion between the polyimide coating film and the base material is an important index for influencing the reliability and the reliability of the chip device, and if the adhesion is poor, the coating film can fall off in the use process of the chip device, so that failure phenomena such as leakage current and the like can be generated. It is therefore important to improve the adhesion of the polyimide coating film to the substrate.

Disclosure of Invention

In order to improve the penetrability of photosensitive polyimide and the adhesive force with a substrate, the application provides a photosensitive polyimide precursor resin, a preparation method and a photosensitive resin composition, wherein the photosensitive polyimide precursor resin is prepared by combining a photosensitive molecular chain block, a silicon-containing molecular chain block and a fluorine-containing molecular chain block, and has photosensitivity, a photosensitive group on a photosensitive diamine monomer can be photodecomposition after ultraviolet light (i line, g line and h line) irradiation, so that the resin solubility is changed, a pattern is displayed in a developing solution, and the transparency of the resin can be further improved by introducing the silicon-containing molecular chain block and the fluorine-containing molecular chain block, so that more chemical rays penetrate through the resin to deep inside the film, thereby being beneficial to improving the photosensitivity.

The photosensitive resin composition prepared by using the photosensitive polyimide precursor resin has the advantages of high sensitivity, high transmittance and high adhesive force, and can be used in the field of semiconductor chip packaging.

In a first aspect, the present application provides a photosensitive polyimide precursor resin

A photosensitive polyimide precursor resin comprising at least one photosensitive molecular chain block, at least one fluorine-containing molecular chain block, and at least one silicon-containing molecular chain block, at least one of the fluorine-containing molecular chain blocks being embedded between the photosensitive molecular chain block and the silicon-containing molecular chain block;

the photosensitive polyimide precursor resin can have the following structures, A-C-B, A-C-A, B-C-B and the like, wherein A represents a photosensitive molecular chain block, B represents a silicon-containing molecular chain segment, and C represents a fluorine-containing molecular chain segment. However, it is not desirable or very few that the silicon-containing molecular chain block is directly connected to the photosensitive molecular chain block, because the inventors found that after the photosensitive composition forms a cured film on a substrate, silicon atoms in the silicon-containing molecular chain segment can form a strong force with the surface of the substrate, especially with the silicon substrate, thereby enhancing the adhesion of the cured film to the substrate, while the photosensitive molecular chain segment is irradiated with ultraviolet light, and the photosensitive group is decomposed to generate a change in solubility, thereby weakening the force of silicon on the molecular chain connected thereto with the substrate when the photosensitive group is dissolved in a developer. Thereby affecting the effectiveness of the silicon-containing molecular chain blocks.

The structural formula of the photosensitive resin molecular chain block is shown as a formula (II);

in the formula (II), M is C ₄ ～C ₄₀ Tetravalent organic radical of R ₁ Is a hydrogen atom, substituted or unsubstituted C ₁ ～C ₂₀ Alkyl, substituted or unsubstituted C ₁ ～C ₂₀ Alkoxy, substituted or unsubstituted C ₆ ～C ₃₀ Aryl radicals R of (2) ₂ Is H atom or C ₁ ～C ₂₀ Q is a photosensitive group, n is an integer of 1 to 5, m ₁ Is an integer of 2 to 200;

preferably, M is C containing an aromatic ring ₆ ～C ₄₀ A tetravalent organic group of (2);

preferably, R ₂ Methyl, ethyl, isopropyl, n-butyl, benzyl or benzyl;

m ₁ is an integer of 20 to 80.

The structural formula of the fluorine-containing resin molecular chain block is shown as a formula (III);

in the formula (III), P ₁ C being fluorine-containing ₂ ～C ₄₀ Is an organic group of (2), M is C ₄ ～C ₄₀ Tetravalent organic radical of R ₂ Is H atom or C ₁ ～C ₂₀ Monovalent organic group, m ₂ Is an integer of 2 to 200;

preferably, M is a compound comprisingC of aromatic ring ₆ ～C ₄₀ A tetravalent organic group of (2);

preferably, R ₂ Selected from methyl, ethyl, isopropyl, n-butyl, benzyl and benzyl;

preferably, m ₂ Is an integer of 20 to 80.

The structural formula of the molecular chain block of the silicon-containing resin is shown as a formula (IV)

In the formula (IV), P ₂ C being silicon-containing ₂ ～C ₄₀ Is an organic group of (2), M is C ₄ ～C ₄₀ Tetravalent organic radical of R ₂ Is H atom or C ₁ ～C ₂₀ Monovalent organic group, m ₃ Is an integer of 2 to 200;

preferably, m ₃ Is an integer of 20 to 80.

Preferably, said R ₁ is-OCF ₃ 。

Preferably, the photosensitive group is

Preferably, the photosensitive molecular chain block is polymerized by dianhydride monomer and photosensitive diamine monomer;

more preferably, the photosensitive diamine monomer is selected from

Preferably, the fluorine-containing molecular chain block is polymerized by dianhydride monomer and fluorine-containing diamine monomer.

More preferably, the fluorochemical diamine monomer is selected from the group consisting of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis [4- (4-aminophenoxyphenyl) ] hexafluoropropane, 2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, 2 '-bis (trifluoromethyl) -4,4' -diaminophenyl ether, N '- (2, 2' -bis (trifluoromethyl) - [1,1 '-biphenyl ] -4,4' -diyl) bis (4-aminobenzamide), 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzene, and 2, 2-bis [ 4-hydroxy-3- (3-amino) benzamide ] hexafluoropropane; preferably, the silicon-containing molecular chain block is polymerized by dianhydride monomer and silicon-containing diamine monomer;

More preferably, the siliceous diamine monomer is selected from the group consisting of 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane, bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethyldisiloxane, bis (p-aminophenyl) tetramethyldisiloxane, bis (gamma-aminopropyl) tetramethyldisiloxane, 1, 4-bis (gamma-aminopropyl dimethylsilanyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (gamma-aminopropyl) tetraphenyldisiloxane, and 1, 3-bis (aminopropyl) tetramethyldisiloxane.

Preferably, the dianhydride monomer is selected from pyromellitic dianhydride, 4' -oxydiphthalic anhydride, 3',4,4' -tetracarboxylic diphenyl dianhydride, 3',4,4' -Tetracarboxydiphenyl sulfone dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride, 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] hexafluoropropane dianhydride, 1, 4-bis (3, 4-dicarboxyphenoxy) benzene dianhydride 1, 3-bis (3, 4-dicarboxyphenoxy) benzene dianhydride, 4' -bis (3, 4-dicarboxyphenoxy) diphenyl sulfone dianhydride, 4' -bis (3, 4-dicarboxyphenoxy) benzophenone dianhydride, 4' -bis (3, 4-dicarboxyphenoxy) biphenyl dianhydride and 4,4' -bis (3, 4-dicarboxyphenoxy) diphenyl ether dianhydride.

In a second aspect, the present application provides a method for preparing a photosensitive polyimide precursor resin, which adopts the following technical scheme:

a process for preparing photosensitive polyimide precursor resin includes such steps as preparing polyimide precursor resin,

preparation of photosensitive fragments: mixing a photosensitive diamine monomer solution with a dianhydride monomer solution, and reacting to obtain a photosensitive fragment;

preparation of fluorine-containing fragment: mixing a fluorine-containing diamine monomer solution with a dianhydride monomer solution, and reacting to obtain a fluorine-containing fragment;

preparation of silicon-containing fragments: mixing a silicon-containing diamine monomer solution with a dianhydride monomer solution, and reacting to obtain a silicon-containing segment;

the sequence of the preparation of the photosensitive segment, the fluorine-containing segment and the silicon-containing segment is not required;

mixing the photosensitive segment, the fluorine-containing segment and the silicon-containing segment, and reacting for 3-24 h at the temperature of 10-100 ℃;

and (3) end capping: adding a blocking agent to carry out a blocking reaction; separation and purification: and pouring the reaction solution after the end capping reaction into deionized water to precipitate a polymer to obtain white precipitate. Filtering the white precipitate, washing with deionized water, and drying at 20-120 deg.c in vacuum for 24-200 hr to obtain photosensitive polyimide precursor resin.

Preferably, the solvent in the photosensitive diamine monomer solution is selected from the group consisting of N-methylpyrrolidone, γ -butyrolactone, tetrahydrofuran, dioxane, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, ethyl acetate, butyl acetate, ethyl lactate, toluene, xylene, diethylene glycol dimethyl ether, and diethylene glycol dimethyl ether;

Optionally, the solvent of the fluorine-containing diamine monomer solution is selected from the group consisting of N-methylpyrrolidone, γ -butyrolactone, tetrahydrofuran, dioxane, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, ethyl acetate, butyl acetate, ethyl lactate, toluene, xylene, diethylene glycol dimethyl ether and diethylene glycol dimethyl ether;

optionally, the solvent of the siliceous diamine monomer solution is selected from the group consisting of N-methylpyrrolidone, γ -butyrolactone, tetrahydrofuran, dioxane, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, ethyl acetate, butyl acetate, ethyl lactate, toluene, xylene, diethylene glycol dimethyl ether, and diethylene glycol dimethyl ether;

optionally, the solvent of the dianhydride monomer solution is selected from the group consisting of N-methylpyrrolidone, γ -butyrolactone, tetrahydrofuran, dioxane, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, ethyl acetate, butyl acetate, ethyl lactate, toluene, xylene, diethylene glycol dimethyl ether and diethylene glycol dimethyl ether.

The solvents used for dissolving the photosensitive diamine monomer, the siliceous diamine monomer, the fluoric diamine monomer and the dianhydride monomer may be the same or different, and in a more preferable case, the same solvent may be selected to dissolve the photosensitive diamine monomer, the siliceous diamine monomer, the fluoric diamine monomer and the dianhydride monomer respectively.

In order to improve the storage stability of the photosensitive resin composition containing the photosensitive diamine monomer, it is preferable to block the main chain end with a blocking agent such as monoamine, acid anhydride, monocarboxylic acid, monoacyl chloride compound, or monoacid ester compound. By reacting a plurality of capping agents, a plurality of different terminal groups may be introduced.

Further monoamines used as end-capping agents are selected from the group consisting of 3-aminophenol, 4-aminophenol, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 3-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4, 6-dihydroxypyrimidine, 3-aminothiophenol and 4-aminothiophenol; the monoanhydride used as the capping agent is selected from the group consisting of phthalic anhydride, itaconic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 4-ethynylphthalic anhydride, methylethylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, and 3-hydroxyphthalic anhydride.

The capping agent may also be selected from the group consisting of 3-carboxyphenol, 4-carboxyphenol, 3-carboxyphenol, 4-carboxythiophenol and 1-hydroxy-7-hydroxynaphthalene.

The above-mentioned blocking agents may be used alone or in combination of 2 or more.

Preferably, the ratio of the amount of the blocking agent to the amount of the dianhydride monomer is (0.01 to 0.5): 1, more preferably, the ratio of the amount of the blocking agent to the amount of the dianhydride monomer is (0.05 to 0.3): 1.

Preferably, after the end-capping step is completed, the product is further esterified: adding an esterification reagent into the product, and reacting for 2-24 h at 30-80 ℃.

By adding the esterification reagent, carboxyl in the resin reacts with the esterification reagent to generate corresponding ester, the prepared photosensitive polyimide precursor resin is polyamide ester, photosensitive groups on a molecular chain are decomposed after exposure and irradiation of the photosensitive composition prepared from the polyamide ester, alkali capacity is greatly improved, patterns can be dissolved and exposed in trampling developer, and a non-exposure area is formed by the fact that the dissolution rate of the polyamide ester in an alkali solution is very low, so that the patterns are left.

Preferably, the esterifying reagent is selected from the group consisting of methanol, ethanol, N-butanol, hydroxyethyl methacrylate, N-dimethylformamide dimethyl acetal, N-dimethylformamide diethyl acetal, and 4-nitrobenzyl alcohol.

The ratio of the amount of the esterifying reagent to the amount of the dianhydride monomer is (1-5): 1, and more preferably the ratio of the amount of the esterifying reagent to the amount of the dianhydride monomer is (1.5-3): 1.

Preferably, when the fluorine-containing segment is blocked by carboxyl, the photosensitive segment and the silicon-containing segment are blocked by amino.

Preferably, when the fluorine-containing segment is blocked by an amino group, the photosensitive segment and the silicon-containing segment are blocked by a carboxyl group.

By controlling the difference of the end capping groups at the two ends of the fluorine-containing molecular chain segment, the photosensitive molecular chain segment and the silicon-containing molecular chain segment, after the photosensitive segment, the fluorine-containing segment and the silicon-containing segment are mixed, the photosensitive segment and the silicon-containing segment are respectively and independently connected at the end of the fluorine-containing segment, so that the connection condition of the photosensitive segment and the silicon-containing segment is reduced, and the photosensitivity and the adhesive force effect of the resin can be improved greatly.

In some embodiments of the present application, a method of preparing a photosensitive polyimide precursor resin may include the steps of: preparation of photosensitive fragments: mixing a photosensitive diamine monomer solution and a dianhydride monomer solution, and reacting for 3-24 hours at the temperature of 10-100 ℃ to obtain a photosensitive fragment;

preparation of fluorine-containing fragment: mixing a fluorine-containing diamine monomer solution with a dianhydride monomer solution, and reacting for 3-24 hours at the temperature of 10-100 ℃ to obtain a fluorine-containing fragment;

preparation of silicon-containing fragments: mixing a silicon-containing diamine monomer solution with a dianhydride monomer solution, and reacting for 3-24 hours at the temperature of 10-100 ℃ to obtain a silicon-containing segment;

the preparation sequence of the photosensitive segment, the fluorine-containing segment and the silicon-containing segment is not required;

And (3) end capping: adding a blocking agent, and reacting for 2-24 hours at the temperature of 10-100 ℃;

esterification: adding an esterification reagent, and reacting for 2-24 hours at the temperature of 30-80 ℃;

separation and purification: and pouring the reaction solution after the end capping reaction into deionized water to precipitate a polymer to obtain white precipitate. Filtering the white precipitate, washing with deionized water, and drying at 20-120 deg.c in vacuum for 24-200 hr to obtain photosensitive polyimide precursor resin.

Preferably, the photosensitive diamine monomer is 5% -40% of the total diamine monomer species involved in the synthesis of the precursor resin, the silicon-containing diamine monomer is 5% -40% of the total diamine monomer species involved in the synthesis of the precursor resin, and the fluorine-containing diamine monomer is 20% -90% of the total diamine monomer species involved in the synthesis of the precursor resin.

More preferably, the photosensitive diamine monomer comprises 10% to 30% of the total diamine monomer species involved in the synthesis of the precursor resin, the silicon-containing diamine monomer comprises 10% to 20% of the total diamine monomer species involved in the synthesis of the precursor resin, and the fluorine-containing diamine monomer comprises 40% to 80% of the total diamine monomer species involved in the synthesis of the precursor resin.

The molar ratio of the total diamine monomer to the total dianhydride monomer is 0.8-1.1: 1, preferably, the molar ratio of total diamine monomer to total dianhydride monomer is from 0.9 to 1.1:1.

the total diamine monomer refers to the total amount of materials of the photosensitive diamine monomer, the silicon-containing diamine monomer and the fluorine-containing diamine monomer, and the total dianhydride monomer refers to the total amount of materials of dianhydrides used in the preparation of the photosensitive segment, the silicon-containing segment and the fluorine-containing segment.

When the photoactive moiety is capped with an amino group, in some embodiments of the present application,

when preparing the photosensitive segment, the mol ratio of the photosensitive diamine monomer to the dianhydride monomer is 1 (0.3-0.8), and the mol ratio of the preferable photosensitive diamine monomer to the dianhydride monomer is 1 (0.4-0.6);

when the silicon-containing segment is end-capped with an amino group, in some embodiments of the present application,

when the silicon-containing segment is prepared, the mol ratio of the silicon-containing diamine monomer to the dianhydride monomer M is 1 (0.3-0.8), and the mol ratio of the preferable photosensitive diamine monomer to the dianhydride monomer is 1 (0.4-0.6);

when the fluorine-containing segment is carboxyl-terminated, in some embodiments of the present application,

when preparing the fluorine-containing fragment, the molar ratio of the fluorine-containing diamine monomer to the dianhydride monomer is 1 (1.4-2.4), and the molar ratio of the photosensitive diamine monomer to the dianhydride monomer is preferably 1 (1.5-2.3).

When the photoactive moiety is carboxyl-terminated, in some embodiments of the present application,

when preparing the photosensitive segment, the mol ratio of the photosensitive diamine monomer to the dianhydride monomer is 1 (1.4-2.4), and the mol ratio of the preferable photosensitive diamine monomer to the dianhydride monomer is 1 (1.5-2.3);

when the silicon-containing segment is carboxyl-terminated, in some embodiments of the present application,

when the silicon-containing fragment is prepared, the mol ratio of the silicon-containing diamine monomer to the dianhydride monomer is 1 (1.4-2.4), and the mol ratio of the preferable photosensitive diamine monomer to the dianhydride monomer is 1 (1.5-2.3);

when the fluorine-containing moiety is end-capped with an amino group, in some embodiments of the present application,

when preparing the fluorine-containing fragment, the molar ratio of the fluorine-containing diamine monomer to the dianhydride monomer is 1 (0.3-0.8), and the molar ratio of the photosensitive diamine monomer to the dianhydride monomer is preferably 1 (0.4-0.6).

In a third aspect, the present application provides a photosensitive resin composition, which adopts the following technical scheme:

a photosensitive resin composition comprising the above photosensitive polyimide precursor resin.

Preferably, the composition further comprises a solvent for dissolving the precursor resin, wherein the weight ratio of the solvent for dissolving the precursor resin to the precursor resin is 10 (7-100), more preferably, the weight ratio of the solvent for dissolving the precursor resin to the precursor resin is 10 (10-50).

Preferably, the solvent used to dissolve the precursor resin is selected from the group consisting of N-methylpyrrolidone, γ -butyrolactone, tetrahydrofuran, dioxane, N-dimethylformamide, dimethylsulfoxide, methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, ethyl lactate, toluene, xylene, diethylene glycol dimethyl ether, and diethylene glycol dimethyl ether.

Preferably, the composition further comprises a leveling agent and/or an antifoaming agent.

Further, the leveling agent is selected from the group consisting of acrylic leveling agents, silicone leveling agents, and fluorine-containing leveling agents.

Preferably, the weight ratio of the leveling agent to the precursor resin is (0.1 to 10): 100

Further, the defoamer is selected from BYK-A530, BYK-A550 and Airex-920.

Preferably, the weight ratio of the antifoaming agent to the precursor resin is (0.1 to 10): 100.

A method for preparing a photosensitive resin composition, comprising the steps of:

and adding the precursor resin into a solvent for dissolving the precursor resin, stirring until the precursor resin is completely dissolved, then adding a leveling agent and/or a defoaming agent, continuously stirring and dissolving, and finally filtering the composition by using a filter with the pore size of 0.1-5 mu m to obtain the photosensitive resin composition.

The viscosity of the photosensitive resin composition is 10 to 10000cP, preferably 100 to 5000cP, more preferably 500 to 4000cP.

In summary, the present application has the following beneficial effects:

1. the photosensitive polyimide precursor resin is obtained by combining the photosensitive molecular chain block, the fluorine-containing molecular chain block and the silicon-containing molecular chain block, can be used for preparing a photosensitive resin composition, and has high adhesive force, high photosensitive performance and high permeability after the prepared photosensitive resin composition is coated into a film.

Detailed Description

The present application is described in further detail below with reference to examples.

The abbreviations used in this application correspond to the compound names (structural formulas) as follows:

a1：

a2：

a3：

a4：

a5：

a6：

b1:2, 2-bis [ 4-hydroxy-3- (3-amino) benzamide ] hexafluoropropane (HFHA);

b2:2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF);

c1:1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane (SIDA);

c2:1, 4-bis (3-aminopropyl dimethylsilyl) benzene;

ODPA:4,4' -oxybisphthalic dianhydride;

6FDA:2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] hexafluoropropane dianhydride;

BTDA:3,3', 4' -tetracarboxylic benzophenone dianhydride;

DSDA:3,3', 4' -tetracarboxylic diphenyl sulfone dianhydride;

DMAC: dimethylacetamide;

NMP: n-methylpyrrolidone.

Preparation examples of the photosensitive diamine monomer and confirmation of the photosensitive diamine monomer

The preparation method of the photosensitive diamine monomer comprises the following steps:

(1) Preparation of the primary product: dissolving hydroxybenzaldehyde and triethylamine in DMAC, adding DMAC solution of diazonaphthol sulfonyl chloride into the system at the temperature of-5 to-3 ℃, stirring, and reacting to obtain a primary product;

(2) Preparation of secondary product: adding hydrochloric acid into the primary product, stirring and filtering to remove triethylamine hydrochloride obtained by triethylamine reaction, then rapidly adding the filtrate into a 0.1% hydrochloric acid aqueous solution at 25 ℃, and fully stirring to obtain yellow-like solid; the yellow-like solid is filtered, washed with deionized water for a plurality of times until the ion content of the washing liquid is below 50ppm, finally washed with absolute ethyl alcohol and dried under reduced pressure at 40 ℃ to obtain a secondary product.

(3) Preparation of crude photosensitive diamine monomer product: mixing the secondary product with aniline hydrochloride and aniline in a 500ml three-neck flask; reacting for 2 hours at 90-110 ℃ in nitrogen atmosphere; then the temperature is raised to 150-170 ℃ and stirred for reaction for 6-8 h; after the reaction, cooling to room temperature to obtain a crude product of the photosensitive diamine monomer.

(4) Purification of crude product of photosensitive diamine monomer: distilling the crude product of the photosensitive diamine monomer at 80 ℃ under reduced pressure to remove excessive aniline; then adding 2mol/L hydrochloric acid solution, fully dissolving and filtering to obtain filtrate; adding 2mol/L sodium hydroxide solution into the filtrate, and carrying out neutralization reaction to obtain an off-white solid after the reaction; the off-white solid was washed with water, recrystallized 2 times with ethanol and dried in vacuo at 80 ℃ to give the product.

Confirmation of photosensitive diamine monomer

Carrying out qualitative analysis on the prepared photosensitive diamine monomer by using an infrared spectrometer; the purity was measured by liquid chromatography.

(1) Infrared spectroscopy testing

The synthesized photosensitive diamine monomer sample was tested using a KBr tabletting method using an infrared spectrometer (Shimadzu, IRAfforescence-1S) to detect whether the desired photosensitive diamine monomer sample was successfully prepared.

If the infrared spectrum is 3400cm ^-1 ～3500cm ^-1 Appearance of-NH at ₂ Asymmetric stretching vibration and symmetric stretching vibration absorption peak of 1370cm ^-1 And 1180cm ^-1 Strong absorption peak of sulfonyl group s=o appears nearby, 2100cm ^-1 The occurrence of an asymmetric stretching vibration absorption peak of the-N=N azide group on the left and right side indicates successful synthesis of the photosensitive diamine monomer, except that the trifluoromethyl group-containing monomer is at 1350cm ^-1 ～1100cm ^-1 The stretching vibration absorption peak of the C-F bond occurs.

(2) Liquid chromatography test

The purity of the synthesized cross-linker was tested using a liquid chromatograph (shimadzu, LC-2030). Chromatographic column: c18; wavelength: 254nm; column incubator: 40 ℃; mobile phase: water: acetonitrile=40: 60; flow rate: 1.0ml/min.

The liquid phase spectrogram has no obvious impurity peak, and the purity is higher than 97% by adopting an integration method.

Combining the infrared spectrum test result and the liquid phase chromatography test result, the photosensitive diamine monomer can be successfully synthesized.

Preparation example 1

Parahydroxyben-zaldehyde (24.43 g,0.2 mol), triethylamine (25.30, 0.25 mol) and DMAC (200 g) were added to a three-necked flask and dissolved by stirring; the reaction system was cooled, and when the internal temperature was-10℃to-5℃a mixed solution of 2-diazonium-1-naphthol-5-sulfonyl chloride (59.55 g,0.22 mol) and DMAC (300 g) was added dropwise to the solution, followed by stirring for 5 hours. To the mixture was added dropwise hydrochloric acid (20 g), followed by stirring for 10min. Separating the triethylamine hydrochloride formed by filtration; the obtained filtrate was rapidly poured into 0.1% aqueous hydrochloric acid (1700 ml) maintained at 20 to 25 ℃. The mixture was stirred well to give a yellow-like solid, which was filtered and the filter cake was washed with deionized water multiple times. Finally, the filter cake was rinsed with absolute ethanol and dried under reduced pressure at 40 ℃.

The above-mentioned product (52.26 g,0.1 mol), aniline hydrochloride (51.80 g,0.4 mol) and aniline (93.20 g,1 mol) were added to a 500ml three-necked flask, heated at 100℃for 2 hours under nitrogen atmosphere, then warmed to 160℃and stirred for 6 hours, cooled to room temperature, distilled off under reduced pressure at 80℃to excess aniline, dissolved and filtered with 2mol.L-1 hydrochloric acid, and the filtrate was neutralized with 2mol.L-1 sodium hydroxide to give an off-white solid, washed with water, recrystallized 2 times with ethanol/water, and dried in vacuo at 80℃to give the product photosensitive diamine monomer a1.

Product validation

3403cm ^-1 Is at the position of-NH ₂ Asymmetric stretching vibration and symmetric stretching vibration absorption peaks; 1374cm ^-1 And 1183cm ^-1 A strong absorption peak for the sulfonyl group s=o; 2085cm ^-1 An asymmetric telescopic vibration absorption peak for an-n=n azide group; the purity of the liquid chromatography is 97.6%

Preparation example 2

4-hydroxy-3-trifluoromethylbenzaldehyde (38.02 g,0.2 mol), triethylamine (25.30 g,0.25 mol) and DMAC (200 g) were charged into a three-necked flask and dissolved by stirring; the reaction system was cooled, and when the internal temperature was between-10℃and-5℃a mixed solution of 2-diazonium-1-naphthol-5-sulfonyl chloride (113.69 g,0.42 mol) and DMAC (300 g) was added dropwise to the solution, followed by stirring. To the mixture was added dropwise hydrochloric acid (20 g), followed by stirring for 10min. Separating the triethylamine hydrochloride formed by filtration; the obtained filtrate was rapidly poured into 0.1% aqueous hydrochloric acid (1700 ml) maintained at 20 to 25 ℃. Fully stirring to obtain yellow-like solid, filtering, washing filter cake with deionized water for several times until the ion content of the washing liquid is below 50 ppm. Finally, the filter cake was rinsed with absolute ethanol and dried under reduced pressure at 40 ℃.

The above-mentioned product (59.06 g,0.1 mol), aniline hydrochloride (51.80 g,0.4 mol) and aniline (93.20 g,1 mol) were added to a 500ml three-necked flask, heated at 100℃for 2 hours under nitrogen atmosphere, then warmed to 160℃and stirred for 6 hours, cooled to room temperature, distilled off under reduced pressure at 80℃to excess aniline, dissolved and filtered with 2mol.L-1 hydrochloric acid, and the filtrate was neutralized with 2mol.L-1 sodium hydroxide to give an off-white solid, washed with water, recrystallized 2 times with ethanol/water, and dried in vacuo at 80℃to give the product photosensitive monomer a2.

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Product validation

3416cm ^-1 Is at the position of-NH ₂ Asymmetric stretching vibration and symmetric stretching vibration absorption peaks; 1372cm ^-1 And 1181cm ^-1 A strong absorption peak for the sulfonyl group s=o; 2102cm ^-1 An asymmetric telescopic vibration absorption peak for an-n=n azide group; 1279cm ^-1 A telescopic vibration absorption peak of C-F bond; the purity by liquid chromatography was 97.8%.

Preparation example 3

4-hydroxy-3-trifluoromethoxybenzaldehyde (41.22 g,0.2 mol), triethylamine (25.30, 0.25 mol) and DMAC (200 g) were added to a three-necked flask, and dissolved by stirring; the reaction system was cooled, and when the internal temperature was between-10℃and-5℃a mixed solution of 2-diazonium-1-naphthol-5-sulfonyl chloride (113.69 g,0.42 mol) and DMAC (300 g) was added dropwise to the solution, followed by stirring. To the mixture was added dropwise hydrochloric acid (20 g), followed by stirring for 10min. Separating the triethylamine hydrochloride formed by filtration; the obtained filtrate was rapidly poured into 0.1% aqueous hydrochloric acid (1700 ml) maintained at 20 to 25 ℃. Fully stirring to obtain yellow-like solid, filtering, washing filter cake with deionized water for several times until the ion content of the washing liquid is below 50 ppm. Finally, the filter cake was rinsed with absolute ethanol and dried under reduced pressure at 40 ℃.

The above-mentioned product (66.66 g,0.1 mol), aniline hydrochloride (51.80 g,0.4 mol) and aniline (93.20 g,1 mol) were added to a 500ml three-necked flask, heated at 100℃for 2 hours under nitrogen atmosphere, then warmed to 160℃and stirred for 6 hours, cooled to room temperature, distilled off under reduced pressure at 80℃to excess aniline, dissolved and filtered with 2mol.L-1 hydrochloric acid, and the filtrate was neutralized with 2mol.L-1 sodium hydroxide to give an off-white solid, washed with water, recrystallized 2 times with ethanol/water, and dried in vacuo at 80℃to give the product photosensitive monomer a3.

Product validation

3415cm ^-1 Is at the position of-NH ₂ Asymmetric stretching vibration and symmetric stretching vibration absorption peaks; 1373cm ^-1 And 1180cm ^-1 A strong absorption peak for the sulfonyl group s=o; 2101cm ^-1 An asymmetric telescopic vibration absorption peak for an-n=n azide group; 1290cm ^-1 A telescopic vibration absorption peak of C-F bond; the purity by liquid chromatography was 97.8%.

Preparation example 4

3, 4-dihydroxybenzaldehyde (27.62 g,0.2 mol), triethylamine (25.30, 0.25 mol) and DMAC (200 g) were added to a three-necked flask and dissolved by stirring; the reaction system was cooled, and when the internal temperature was between-10℃and-5℃a mixed solution of 2-diazonium-1-naphthol-5-sulfonyl chloride (113.69 g,0.42 mol) and DMAc (300 g) was added dropwise to the solution, followed by stirring. To the mixture was added dropwise hydrochloric acid (20 g), followed by stirring for 10min. Separating the triethylamine hydrochloride formed by filtration; the obtained filtrate was rapidly poured into 0.1% aqueous hydrochloric acid (1700 ml) maintained at 20 to 25 ℃. Fully stirring to obtain yellow-like solid, filtering, washing filter cake with deionized water for several times until the ion content of the washing liquid is below 50 ppm. Finally, the filter cake was rinsed with absolute ethanol and dried under reduced pressure at 40 ℃.

The above-mentioned product (77.08 g,0.1 mol), aniline hydrochloride (51.80 g,0.4 mol) and aniline (93.20 g,1 mol) were added to a 500ml three-necked flask, heated at 100℃for 2 hours under nitrogen atmosphere, then warmed to 160℃and stirred for 6 hours, cooled to room temperature, distilled off under reduced pressure at 80℃to excess aniline, dissolved and filtered with 2mol.L-1 hydrochloric acid, and the filtrate was neutralized with 2mol.L-1 sodium hydroxide to give an off-white solid, washed with water, recrystallized 2 times with ethanol/water, and dried in vacuo at 80℃to give the product photosensitive monomer a4.

Product validation

3425cm ^-1 Is at the position of-NH ₂ Asymmetric stretching vibration and symmetric stretching vibration absorption peaks; 1376cm ^-1 And 1189cm ^-1 A strong absorption peak for the sulfonyl group s=o; 2096cm ^-1 An asymmetric telescopic vibration absorption peak for an-n=n azide group; the purity by liquid chromatography was 97.3%.

Preparation example 5

4-hydroxy-3-trifluoromethoxybenzaldehyde (41.22 g,0.2 mol) triethylamine (25.30, 0.25 mol) and DMAC (200 g) were added to a three-necked flask, and dissolved by stirring; the reaction system was cooled, and when the internal temperature was between-10℃and-5℃a mixed solution of 2-diazonium-1-naphthol-4-sulfonyl chloride (113.69 g,0.42 mol) and DMAc (300 g) was added dropwise to the solution, followed by stirring. To the mixture was added dropwise hydrochloric acid (20 g), followed by stirring for 10min. Separating the triethylamine hydrochloride formed by filtration; the obtained filtrate was rapidly poured into 0.1% aqueous hydrochloric acid (1700 ml) maintained at 20 to 25 ℃. Fully stirring to obtain yellow-like solid, filtering, washing filter cake with deionized water for several times until the ion content of the washing liquid is below 50 ppm. Finally, the filter cake was rinsed with absolute ethanol and dried under reduced pressure at 40 ℃.

The above-mentioned product (66.66 g,0.1 mol), aniline hydrochloride (51.80 g,0.4 mol) and aniline (93.20 g,1 mol) were added to a 500ml three-necked flask, heated at 100℃for 2 hours under nitrogen atmosphere, then warmed to 160℃and stirred for 6 hours, cooled to room temperature, distilled off under reduced pressure at 80℃to excess aniline, dissolved and filtered with 2mol.L-1 hydrochloric acid, and the filtrate was neutralized with 2mol.L-1 sodium hydroxide to give an off-white solid, washed with water, recrystallized 2 times with ethanol/water, and dried in vacuo at 80℃to give the product photosensitive monomer a5.

Product validation

3415cm ^-1 Is at the position of-NH ₂ Asymmetric stretching vibration and symmetric stretching vibration absorption peaks; 1365cm ^-1 And 1173cm ^-1 A strong absorption peak for the sulfonyl group s=o; 2115cm ^-1 An asymmetric telescopic vibration absorption peak for an-n=n azide group; 1291cm ^-1 A telescopic vibration absorption peak of C-F bond; the purity by liquid chromatography was 97.5%.

Preparation example 6

3, 4-dihydroxybenzaldehyde (27.62 g,0.2 mol) triethylamine (25.30, 0.25 mol) and DMAC (200 g) were added to a three-necked flask and dissolved by stirring; the reaction system was cooled, and when the internal temperature was between-10℃and-5℃a mixed solution of 2-diazonium-1-naphthol-4-sulfonyl chloride (56.85 g,0.21 mol), 2-diazonium-1-naphthol-5-sulfonyl chloride (56.85 g,0.21 mol) and DMAc (300 g) was added dropwise to the solution, followed by stirring. To the mixture was added dropwise hydrochloric acid (20 g), followed by stirring for 10min. Separating the triethylamine hydrochloride formed by filtration; the obtained filtrate was rapidly poured into 0.1% aqueous hydrochloric acid (1700 ml) maintained at 20 to 25 ℃. Fully stirring to obtain yellow-like solid, filtering, washing filter cake with deionized water for several times until the ion content of the washing liquid is below 50 ppm. Finally, the filter cake was rinsed with absolute ethanol and dried under reduced pressure at 40 ℃.

The above-mentioned product (77.08 g,0.1 mol), aniline hydrochloride (51.80 g,0.4 mol) and aniline (93.20 g,1 mol) were added to a 500ml three-necked flask, heated at 100℃for 2 hours under nitrogen atmosphere, then warmed to 160℃and stirred for 6 hours, cooled to room temperature, distilled off under reduced pressure at 80℃to excess aniline, dissolved and filtered with 2mol.L-1 hydrochloric acid, and the filtrate was neutralized with 2mol.L-1 sodium hydroxide to give an off-white solid, washed with water, recrystallized 2 times with ethanol/water, and dried in vacuo at 80℃to give the product photosensitive monomer a6.

5-naphthoquinone diazide sulfonic acid and 4-naphthoquinone diazide sulfonic acid are all possible to react in ortho or para positions without selectivity, so a6 is a mixture of a6-1 and a 6-2.

Product validation

3415cm ^-1 The asymmetric stretching vibration and symmetric stretching vibration absorption peak of-NH 2; 1368cm ^-1 And 1176cm ^-1 A strong absorption peak for the sulfonyl group s=o; 2103cm ^-1 An asymmetric telescopic vibration absorption peak for an-n=n azide group; the purity by liquid chromatography was 97.2%.

Preparation of photosensitive polyimide precursor resin

A method for preparing a photosensitive polyimide precursor resin, comprising the steps of:

preparation of photosensitive fragments: mixing a photosensitive diamine monomer solution and a dianhydride monomer solution, and reacting for 3-24 hours at the temperature of 10-100 ℃ to obtain a photosensitive fragment;

Example 1

Preparation of amino-terminated photoactive fragment:

4.65g (0.015 mol) of ODPA and 10g of NMP were placed in a 250mL three-necked flask and dissolved by stirring. A diamine solution of 15.68g (0.03 mol) of the photosensitive diamine monomer a1 and 30.00g of NMP was then dropped thereinto, and reacted at 80℃for 3 hours.

Preparation of amino-terminated silicon-containing fragment:

3.10g (0.01 mol) of ODPA and 10g of NMP were placed in a 250mL three-necked flask and dissolved by stirring. A diamine solution of 4.97g (0.02 mol) of SIDA and 20.00g of NMP was then added dropwise thereto, and the mixture was reacted at 80℃for 3 hours.

Preparation of carboxyl-terminated fluorine-containing fragment:

23.27g (0.075 mol) of ODPA and 50.00g of NMP were placed in a 500mL three-necked flask and dissolved by stirring. A mixed solution of 24.18g (0.04 mol) of HFHA and 50.00g of NMP was then added dropwise thereto, and the mixture was reacted at 80℃for 3 hours.

The reaction solution 1, the reaction solution 2 and the reaction solution 3 were mixed in the same 500ml reaction flask and reacted at 50℃for 6 hours. After completion of the reaction, 2.18g (0.02 mol) of 3-aminophenol as a blocking agent was added thereto and reacted at 50℃for 2 hours. Then, a solution of 23.83g (0.2 mol) of N, N-dimethylformamide dimethyl acetal diluted with 45.00g of NMP was added dropwise thereto, and the mixture was reacted at 50℃for 3 hours after completion of the addition. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and the polymer is separated out to obtain white precipitate. Filtering, washing with deionized water for three times, and drying in vacuum oven at 80deg.C for 72hr to obtain polyesteramide.

Example 2

Is different from example 1 in that

15.68g (0.03 mol) of the photosensitive diamine monomer a1 was replaced with 17.72g (0.03 mol) of the photosensitive diamine monomer a2.

Example 3

Is different from example 1 in that

15.68g (0.03 mol) of the photosensitive diamine monomer a1 was replaced with 18.20g (0.03 mol) of the photosensitive diamine monomer a2.

Example 4

Is different from example 1 in that

15.68g (0.03 mol) of the photosensitive diamine monomer a1 was replaced with 23.12g (0.03 mol) of the photosensitive diamine monomer a4.

Example 5

Is different from example 1 in that

15.68g (0.03 mol) of the photosensitive diamine monomer a1 was replaced with 18.20g (0.03 mol) of the photosensitive diamine monomer a5.

Example 6

Is different from example 1 in that

15.68g (0.03 mol) of the photosensitive diamine monomer a1 was replaced with 23.12g (0.03 mol) of the photosensitive diamine monomer a6.

Example 7

Is different from example 3 in that

4.97g (0.02 mol) of SIDA were exchanged for 6.17g (0.02 mol) of 1, 4-bis (3-aminopropyl dimethylsilyl) benzene.

Example 8

Is different from example 3 in that

24.18g (0.04 mol) of HFHA was replaced by 14.65g (0.04 mol) of BAHF.

Example 9

Is different from example 3 in that

Preparation of amino-terminated silicon-containing fragment:

4.44g (0.01 mol) of 6FDA and 10g of NMP were placed in a 250mL three-necked flask and dissolved by stirring. A diamine solution of 4.97g (0.02 mol) of SIDA and 20.00g of NMP was then added dropwise thereto, and the mixture was reacted at 80℃for 3 hours.

Example 10

Preparation of amino-terminated photoactive fragment:

4.65g (0.015 mol) of ODPA and 10g of NMP were placed in a 250mL three-necked flask and dissolved by stirring. Then, a diamine solution of 18.20g (0.03 mol) of the photosensitive diamine monomer a3 and 30.00g of NMP was dropped thereinto, and reacted at 80℃for 3 hours.

Preparation of amino-terminated silicon-containing fragment:

Preparation of carboxyl-terminated fluorine-containing fragment:

24.17g (0.075 mol) of BTDA and 50.00g of NMP were placed in a 500mL three-necked flask and dissolved by stirring. A mixed solution of 24.18g (0.04 mol) of HFHA and 50.00g of NMP was then added dropwise thereto, and the mixture was reacted at 80℃for 3 hours.

Example 11

Preparation of amino-terminated photoactive fragment:

5.37g (0.015 mol) of DSDA and 10g of NMP were placed in a 250mL three-necked flask and dissolved with stirring. Then, a diamine solution of 18.20g (0.03 mol) of the photosensitive diamine monomer a3 and 30.00g of NMP was dropped thereinto, and reacted at 80℃for 3 hours.

Preparation of amino-terminated silicon-containing fragment:

Preparation of carboxyl-terminated fluorine-containing fragment:

Example 12

Is different from example 3 in that

23.83g (0.2 mol) of N, N-dimethylformamide dimethyl acetal was replaced with 29.44g (0.2 mol) of N, N-dimethylformamide diethyl acetal.

Example 13

Preparation of carboxyl-terminated photoactive fragment:

13.96g (0.045 mol) of ODPA and 10g of NMP were placed in a 250mL three-necked flask and dissolved by stirring. Then, a diamine solution of 18.20g (0.03 mol) of the photosensitive diamine monomer a3 and 30.00g of NMP was dropped thereinto, and reacted at 80℃for 3 hours.

Preparation of carboxyl-terminated silicon-containing fragment:

10.55 (0.035 mol) of ODPA and 10g of NMP were placed in a 250mL three-necked flask and dissolved by stirring. A diamine solution of 4.97g (0.02 mol) of SIDA and 20.00g of NMP was then added dropwise thereto, and the mixture was reacted at 80℃for 3 hours.

Preparation of amino-terminated fluorine-containing fragment:

6.20g (0.02 mol) of ODPA and 50.00g of NMP were placed in a 500mL three-necked flask and dissolved by stirring. A mixed solution of 24.18g (0.04 mol) of HFHA and 50.00g of NMP was then added dropwise thereto, and the mixture was reacted at 80℃for 3 hours.

Example 14

Differing from example 13

Preparation of carboxyl-terminated silicon-containing fragment:

15.5g (0.035 mol) of 6FDA and 10g of NMP were placed in a 250mL three-necked flask and dissolved by stirring. A diamine solution of 4.97g (0.02 mol) of SIDA and 20.00g of NMP was then added dropwise thereto, and the mixture was reacted at 80℃for 3 hours.

Preparation of amino-terminated fluorine-containing fragment:

6.44g (0.02 mol) of ODPA and 50.00g of NMP were placed in a 500mL three-necked flask and dissolved by stirring. A mixed solution of 24.18g (0.04 mol) of HFHA and 50.00g of NMP was then added dropwise thereto, and the mixture was reacted at 80℃for 3 hours.

Example 15

Preparation of amino-terminated photoactive fragment:

Preparation of amino-terminated silicon-containing fragment:

1.55g (0.005 mol) of ODPA and 10g of NMP were placed in a 250mL three-necked flask and dissolved by stirring. A diamine solution of 2.49g (0.01 mol) of SIDA and 20.00g of NMP was then added dropwise thereto, and the mixture was reacted at 80℃for 3 hours.

Preparation of carboxyl-terminated fluorine-containing fragment:

24.82g (0.08 mol) of ODPA and 50.00g of NMP were placed in a 500mL three-necked flask and dissolved by stirring. A mixed solution of 30.23g (0.05 mol) of HFHA and 50.00g of NMP was then added dropwise thereto, and the mixture was reacted at 80℃for 3 hours.

Example 16

Preparation of amino-terminated photoactive fragment:

1.55g (0.005 mol) of ODPA and 10g of NMP were placed in a 250mL three-necked flask and dissolved by stirring. A diamine solution of 6.07g (0.01 mol) of the photosensitive diamine monomer a3 and 30.00g of NMP was then dropped thereinto, and reacted at 80℃for 3 hours.

Preparation of amino-terminated silicon-containing fragment:

Preparation of carboxyl-terminated fluorine-containing fragment:

26.37g (0.085 mol) of ODPA and 50.00g of NMP were placed in a 500mL three-necked flask and dissolved by stirring. A mixed solution of 36.28g (0.06 mol) of HFHA and 50.00g of NMP was then added dropwise thereto, and the mixture was reacted at 80℃for 3 hours.

Example 17

Preparation of amino-terminated photoactive fragment:

Preparation of amino-terminated silicon-containing fragment:

Preparation of carboxyl-terminated fluorine-containing fragment:

27.92g (0.09 mol) of ODPA and 50.00g of NMP were placed in a 500mL three-necked flask and dissolved by stirring. A mixed solution of 42.33g (0.07 mol) of HFHA and 50.00g of NMP was then added dropwise thereto, and the mixture was reacted at 80℃for 3 hours.

Comparative example

Comparative example 1

31.02g (0.1 mol) of ODPA and 70.00-g N-methylpyrrolidone (NMP) were placed in a 500mL three-necked flask, and the mixture was dissolved by stirring to obtain a dianhydride solution. A diamine mixture solution composed of 15.68g (0.03 mol) of the photosensitive diamine monomer a3, 24.18g (0.04 mol) of HFHA, 4.97g (0.02 mol) of SIDA and 100.00. 100.00g N-methylpyrrolidone (NMP) was then added dropwise thereto, and the mixture was reacted at 80℃for 3 hours after the completion of the addition.

After completion of the reaction, 2.18g (0.02 mol) of 3-aminophenol as a blocking agent was added thereto and reacted at 50℃for 2 hours. Then, a solution of 23.83g (0.2 mol) of N, N-dimethylformamide dimethyl acetal diluted with 45.00g of NMP was added dropwise thereto, and the mixture was reacted at 50℃for 3 hours after completion of the addition. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and the polymer is separated out to obtain white precipitate. Washing with deionized water for three times after filtering, and putting the mixture into a vacuum oven for drying at 80 ℃ for 72 hours to obtain polyesteramide.

Comparative example 2

Preparation of amino-terminated silicon-containing fragment:

Preparation of carboxyl-terminated fluorine-containing fragment:

The reaction solution 1 and the reaction solution 2 were mixed in the same 500ml reaction flask and reacted at 50℃for 6 hours. After completion of the reaction, 2.18g (0.02 mol) of 3-aminophenol as a blocking agent was added thereto and reacted at 50℃for 2 hours. Then, a solution of 23.83g (0.2 mol) of N, N-dimethylformamide dimethyl acetal diluted with 45.00g of NMP was added dropwise thereto, and the mixture was reacted at 50℃for 3 hours after completion of the addition. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and the polymer is separated out to obtain white precipitate. Filtering, washing with deionized water for three times, and drying in vacuum oven at 80deg.C for 72hr to obtain polyesteramide.

Comparative example 3

Preparation of amino-terminated photoactive fragment:

Preparation of carboxyl-terminated fluorine-containing fragment:

Comparative example 4

31.02g (0.1 mol) of ODPA and 70.00-g N-methylpyrrolidone (NMP) were placed in a 500mL three-necked flask, and the mixture was dissolved by stirring to obtain a dianhydride solution. Then, a diamine mixture solution of 54.41g (0.09 mol) of HFHA and 150.00: 150.00g N-methylpyrrolidone (NMP) was added dropwise thereto, and the mixture was reacted at 80℃for 3 hours after completion of the addition.

TABLE 1 examples 1-8, comparative examples 1-4 raw materials and amounts

Note that: and/indicates that no addition was made.

Preparation of photosensitive resin composition

Application examples 1 to 17, and comparative application examples 1 to 4 were prepared by the following methods

In a three-necked flask equipped with stirring, 100.00g of the synthesized block photosensitive polyimide precursor resin was dissolved in 200.00g of N-methylpyrrolidone (NMP), after complete dissolution, 2.50g of a leveling agent BYK-392 and 2.50g of a defoaming agent BYK-A530 were added, stirring was continued until complete dissolution, and then press filtration was carried out with a 1.0 μm filter membrane to obtain a photosensitive resin composition.

Comparative application example 5 preparation method of block type photosensitive resin composition:

in a three-necked flask equipped with stirring, 100.00g of the block type polyimide precursor resin obtained in comparative example 2 was dissolved in 200.00g of NMP, after complete dissolution, 20g of a sensitizer quinone diazide compound NT-300 (manufactured by Toyo Seisakusho Kogyo Co., ltd.), 2.50g of a leveling agent BYK-392, and 2.50g of a defoamer BYK-A530 were added, and after continuing stirring until complete dissolution, press filtration was carried out with a 1.0 μm filter membrane, to obtain a photosensitive resin composition.

Comparative application example 6 preparation method of block type photosensitive resin composition:

in a three-necked flask equipped with stirring, 100.00g of the block type polyimide precursor resin obtained in comparative example 3 was dissolved in 200.00g of NMP, after complete dissolution, 5.00g of 3- (triethoxysilylthio) propyltrimethoxysilane (Japanese Kogyo chemical, X-12-1056 ES), 2.50g of leveling agent BYK-392,2.50g of defoaming agent BYK-A530 were added, and after continuing stirring until complete dissolution, filtration was carried out with a 1.0 μm filter membrane to obtain a photosensitive resin composition.

Comparative application example 7 preparation method of block type photosensitive resin composition:

in a three-necked flask equipped with stirring, 100.00g of the block type polyimide precursor resin obtained in comparative example 4 was dissolved in 200.00g of NMP, after complete dissolution, 20g of a sensitizer quinone diazide compound NT-300 (manufactured by Toyo Seisakusho Kogyo Co., ltd.), 5.00g of 3- (triethoxysilylthio) propyltrimethoxysilane (Japanese Kogyo Chemie, X-12-1056 ES), 2.50g of a leveling agent BYK-392,2.50g of an antifoaming agent BYK-A530 were added, and after continuing stirring until complete dissolution, filtration was carried out with a 1.0 μm filter membrane to obtain a photosensitive resin composition.

TABLE 2 correspondence between precursor resins used in application examples 1 to 17 and comparative application examples 1 to 7 and examples 1 to 17 and comparative examples 1 to 4

Performance test

1. Measurement of weight average molecular weight (Mw) and molecular weight distribution (PDI) of Block photosensitive polyimide precursor resin the weight average molecular weight (Mw) and molecular weight distribution (PDI) of the resin were measured by gel permeation chromatography (standard polystyrene conversion). The gel permeation chromatograph used in the measurement was LC-20AD of Shimadzu corporation, the column was KF-804 of Showa electrician, the detector was differential RID-20A of Shimadzu corporation, and the mobile phase was N-methylpyrrolidone (NMP).

2. Block type photosensitive resin composition viscosity test

A sample of 0.5ml was placed in a rotary viscometer (BROOKFIELD DV2T RV) sample cell, and the temperature was controlled at 25.+ -. 0.1 ℃ for viscosity testing.

3. Viscosity i-line transmittance test of block type photosensitive resin composition

The block type photosensitive precursor resin composition was spin-coated uniformly on a glass sheet using a spin coater (EZ 4, lei Bo technology), dried at 120 ℃ for 3 minutes on a hot plate (NDK-2K, japan), and a coating film having a film thickness of 7 μm was obtained by adjusting the spin-coating rotation speed. The transmittance of the coating film was measured by an ultraviolet-visible spectrometer (UV-2600, shimadzu), and the wavelength was 365nm.

The photosensitive resin composition is coated on a silicon wafer, and the light transmittance at 365nm wavelength is required to be 5% or more per 5 μm thick film. If the transmittance of the film is high, more chemical rays reach deep inside the film, thereby contributing to the improvement of the photosensitivity.

4. Dissolution rate of exposed and non-exposed areas of block photosensitive resin composition

A sample of the photosensitive resin composition was coated on a 4-inch silicon wafer, followed by soft baking at 120℃for 3 minutes using a heating table (NDK-2K, japan), the film thickness of a was measured by a step machine (P-7, KLA-Tencor, U.S.) and then the above silicon wafer was placed on an exposure machine (BG-401A, forty-five institute of China electronics and technology group Co., ltd.), a mask was placed, 365nm light (i-line) was selected, and 250mJ/cm was used ² The photosensitive resin film is exposed to the energy of (a). The exposed silicon wafer is put into alkaline developer (2.38% TMAH aqueous solution) for development, and the temperature is controlled at 25+/-1 ℃. Recording a 50 micron line and space (1L/1S) pattern with a development time T of 1:1 width ₁ The coating adhesive falling time of the non-exposure area is T ₂ 。

The dissolution rate of the exposed area was calculated by the following formula:

the dissolution rate of the exposure area is below 9 s/mu m, which can meet the application.

The dissolution rate of the non-exposed areas was calculated by the following formula:

the dissolution rate of the non-exposure area is more than 30 s/mu m, which can meet the application.

5. Imidization film retention rate measurement of block type photosensitive resin composition

The photosensitive resin composition was spin-coated uniformly on a glass sheet using a spin coater (EZ 4, lei Bo technology) at 3000r and dried on a hot plate (NDK-2K, japan) at 120℃for 3 minutes. The film thickness was measured to be N by a step machine (P-7, U.S. KLA-Tencor) ₁ . Placing the pre-baked silicon wafer in a vacuum anaerobic oven (MOLZK-32D 1, combined fertilizer and vacuum electron), heating to 180deg.C for 1 hr heat treatment, heating to 250deg.C for 1 hr heat treatment for 20 min, heating to 300deg.C for 20 min, continuing heat treatment for 1.5 hr, and obtaining cured film, and measuring film thickness N ₂ 。

The imidization film retention rate was calculated by the following formula:

6. imidization test of cured film

Infrared spectra of the cured films at curing temperatures of 300℃and 350℃were measured by an ATR method using an infrared spectrometer (Shimadzu, IRAfforescence-1S), and 1380cm was recorded ^-1 Intensity A of the stretching vibration absorption peak of C-N bond and 1500cm ^-1 Absorption peak intensity a of benzene ring at the position.

The calculation formula of the imidization degree alpha is as follows:

7. adhesion peel test of cured film of Block photosensitive resin composition and substrate

A sample of the resin composition was uniformly coated on a copper substrate by a spin coater, and the coated substrate was soft-baked at 120℃for 3 minutes on a heating table to obtain a resin film having a film thickness of 10 to 20. Mu.m. The resin film was patterned into 10 rows by 10 columns of squares using a dicer (BYK-Gardner a-5125), and then the film was placed in a vacuum oxygen-free oven (MOLZK-32D 1) for heat treatment: after heat treatment at 170℃for 30 minutes, the temperature was raised to 320℃over 1 hour, and the cured film was finally obtained after treatment at 320℃for 1 hour. The cured films were placed in a PCT test chamber and subjected to PCT aging test (121 ℃ C., 2 atm saturated steam; dongguan Hongyan science and technology PCT-30) for 200 hours/300 hours, respectively, and after the PCT test was completed, a peeling test was performed by using an adhesive tape (a special transparent 3M adhesive tape) with reference to the cross-cut test of the national standard GB/T9286-1998 colored paint and varnish film, and the number of peeled-off portions was recorded as peeling conditions after the PCT test.

The number of peels in the adhesion peel test was regarded as "optimum" when the number was less than 5, as "good" when the number was less than 10, as "slightly good" when the number was less than 30, and as "poor" when the number was 30 or more.

The weight average molecular weight and molecular weight distribution of the photosensitive polyimide precursor resin are shown in Table 3

TABLE 3 weight average molecular weight (Mw) and molecular weight distribution (PDI) of precursor resins

Performance test of the block type photosensitive resin composition is shown in Table 4

TABLE 4 detection of Block type photosensitive resin composition Properties

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As can be seen from table 4, the photosensitive resin composition was further prepared by combining the photosensitive molecular chain block, the fluorine-containing molecular chain block, and the silicon-containing molecular chain block according to a specific structure. The film formed by coating the composition on the surface of the substrate has high transmittance and high adhesive force. By combining application examples 1-17, the transmittance can reach more than 8.4%; the number of stripping in 200 hours is not more than 3, and the number of stripping in 300 hours is not more than 9.

When the film is subjected to photosensitive etching, the dissolution rate of the exposure area is not more than 4.5s/μm, and the dissolution rate of the non-exposure area is not less than 43.1s/μm. So that the film can respond quickly to the exposure and a clear image can be obtained.

Wherein the imidization rate in application example 3 reaches 99%, and the i-line transmittance reaches 9%; the number of peeled sheets was 0 after PCT-200 hours, and 1 after PCT-300 hours.

In application example 10, the dissolution rate of the exposed region was 3.7 s/. Mu.m, and the dissolution rate of the non-exposed region was 52.9 s/. Mu.m.

In combination of application examples 1 to 6 and comparative application examples 2 to 7, the photosensitive molecular chain blocks and/or the silicon-containing molecular chain blocks are respectively connected to the ends of the fluorine-containing molecular chain blocks in application examples 1 to 6; in contrast, in comparative examples 2 to 4, no photo-labile molecular chain blocks and/or silicon-containing molecular chain blocks were added; comparative application examples 5 to 7 did not add the photoactive molecular building blocks and/or the silicon-containing molecular chain blocks but instead supplemented the corresponding photoactive agents and/or silane-based additives. By comparison, it was found that films prepared using the precursor resins of examples 1 to 6 had better transmittance and adhesion than films prepared using comparative examples 2 to 4 and mixing the sensitizer and/or the silane-based additive. The i-line transmittance, the number of peeled-off sheets after PCT-200 hours, and the number of peeled-off sheets after PCT-300 hours in application examples 1-6 are all significantly better than those in comparative application examples 2-7.

Referring to application examples 1 to 6 and comparative example 1, it can be seen that each of the properties in application examples 1 to 6 obtained by defining the specific structure of the precursor resin, i.e., the connection relationship between the photosensitive molecular chain block, the silicon-containing molecular chain block, and the fluorine-containing molecular chain block, is significantly superior to that of comparative application example 1 obtained by random copolymerization.

Referring to application examples 3 and 13, application examples 10 and 14, it can be seen that the molar ratio of the dianhydride monomer to the diamine monomer is controlled such that the diamine monomer or the dianhydride monomer is excessive, thereby controlling whether the molecular chain block is terminated by carboxyl group or amino group, and further controlling the connection form of the photosensitive molecular chain block, the silicon-containing molecular chain block and the fluorine-containing molecular chain block in the precursor resin. The use of amino-or carboxyl-terminated groups for the same molecular chain block has little effect on the overall properties of the precursor resin, but it can be seen from application examples 3 and 13 that when the photosensitive segment is amino-terminated, the silicon-containing segment is amino-terminated, and the fluorine-containing segment is carboxyl-terminated, the resulting precursor resin has better properties, and the film of application example 3 has better permeability and better adhesion than application example 13 (after PCT-200h, the number of peeled applications example 3 is the same as application example 13, and after PCT-300h, the number of peeled applications example 3 is smaller than application example 13).

The proportion of the photosensitive molecular continuous block, the silicon-containing molecular chain block and the fluorine-containing molecular chain block in the precursor resin can be controlled by adjusting the dosage of the photosensitive diamine monomer, the silicon-containing diamine monomer and the fluorine-containing diamine monomer.

Referring to examples 3 and 15, an increase in the amount of the silicon-containing diamine monomer and a decrease in the amount of the fluorine-containing diamine monomer resulted in an increase in the proportion of the silicon-containing molecular chain block in the total amount (by weight) of the precursor resin in the corresponding obtained precursor resin and a decrease in the proportion of the fluorine-containing molecular chain block in the total amount (by weight) of the precursor resin; referring to application examples 3 and 15, an increased proportion of the silicon-containing molecular chain block to the total amount (weight) of the precursor resin contributes to an improvement in the adhesion of the film to the substrate.

Referring to examples 3 and 16, the increase in the amount of the photosensitive monomer and the decrease in the amount of the fluorine-containing monomer, the ratio of the photosensitive molecular chain block to the total amount (weight) of the precursor resin in the obtained precursor resin becomes large, and the ratio of the fluorine-containing molecular chain block to the total amount (weight) of the precursor resin becomes small; referring to application examples 3 and 16, an increase in the proportion of the photosensitive molecular chain block to the total amount (weight) of the precursor resin contributes to an improvement in the reduction of the dissolution rate by exposure and an improvement in the transmittance.

The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.

Claims

1. A photosensitive polyimide precursor resin, characterized in that the precursor resin comprises at least one photosensitive molecular chain block, at least one fluorine-containing molecular chain block, and at least one silicon-containing molecular chain block, wherein at least one fluorine-containing molecular chain block is embedded between the photosensitive molecular chain block and the silicon-containing molecular chain block;

the structural formula of the photosensitive molecular chain block is shown as a formula (II);

in the formula (II), M is C ₄ ～C ₄₀ Tetravalent organic radical of R ₁ Is a hydrogen atom, substituted or unsubstituted C ₁ ～C ₂₀ Alkyl, substituted or unsubstituted C ₁ ～C ₂₀ Alkoxy, substituted or unsubstituted C ₆ ～C ₃₀ Aryl radicals R of (2) ₂ Is H atom or C ₁ ～C ₂₀ N is an integer of 1 to 5, Q is a photosensitive group, m ₁ Is an integer of 2 to 200;

the structural formula of the fluorine-containing molecular chain block is shown as a formula (III);

in the formula (III), P ₁ C being fluorine-containing ₂ ～C ₄₀ Is an organic group of (2), M is C ₄ ～C ₄₀ Tetravalent organic radical of R ₂ Is H atom or C ₁ ～C ₂₀ Monovalent organic group, m ₂ Is an integer of 2 to 200,

the structural formula of the silicon-containing molecular chain block is shown as a formula (IV)

In the formula (IV), P ₂ C being silicon-containing ₂ ～C ₄₀ Is an organic group of (2), M is C ₄ ～C ₄₀ Tetravalent organic radical of R ₂ Is H atom or C ₁ ～C ₂₀ Monovalent organic group, m ₃ Is an integer of 2 to 200.

2. The photosensitive polyimide precursor resin according to claim 1, wherein: the R is ₁ is-OCF ₃ 。

3. The photosensitive polyimide precursor resin according to claim 1, wherein the photosensitive group is

4. The photosensitive polyimide precursor resin according to claim 1, wherein the photosensitive molecular chain block is polymerized from a dianhydride monomer and a photosensitive diamine monomer;

optionally, the silicon-containing molecular chain block is polymerized by dianhydride monomer and silicon-containing diamine monomer;

optionally, the fluorine-containing molecular chain block is polymerized by dianhydride monomer and fluorine-containing diamine monomer.

5. The photosensitive polyimide precursor resin according to claim 4, wherein said photosensitive diamine monomer is selected from the group consisting of

6. The photosensitive polyimide precursor resin according to claim 4, wherein,

the fluorine-containing diamine monomer is selected from the group consisting of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis [4- (4-aminophenoxyphenyl) ] hexafluoropropane, 2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, 2 '-bis (trifluoromethyl) -4,4' -diaminophenyl ether, N '- (2, 2' -bis (trifluoromethyl) - [1,1 '-biphenyl ] -4,4' -diyl) bis (4-aminobenzamide), 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzene, and 2, 2-bis [ 4-hydroxy-3- (3-amino) benzamide ] hexafluoropropane.

7. The photosensitive polyimide precursor resin according to claim 4, wherein,

the siliceous diamine monomer is selected from the group consisting of 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane, bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethyldisiloxane, bis (p-aminophenyl) tetramethyldisiloxane, bis (gamma-aminopropyl) tetramethyldisiloxane, 1, 4-bis (gamma-aminopropyl dimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (gamma-aminopropyl) tetraphenyldisiloxane, and 1, 3-bis (aminopropyl) tetramethyldisiloxane.

8. A method for producing a photosensitive polyimide precursor resin according to any one of claim 1 to 7, comprising the steps of,

mixing the photosensitive segment, the fluorine-containing segment and the silicon-containing segment, and reacting for 3-24 h at the temperature of 10-100 ℃; then adding a blocking agent to carry out a blocking reaction;

Separation and purification: pouring the reaction solution after the end-capping reaction into deionized water, precipitating the polymer to obtain white precipitate, filtering the white precipitate, washing the white precipitate with deionized water, and then drying the white precipitate for 36-120 h under the vacuum condition of 40-100 ℃ to obtain the photosensitive polyimide precursor resin.

9. The method for producing a photosensitive polyimide precursor resin according to claim 8, wherein the solvent in the photosensitive diamine monomer solution is selected from the group consisting of N-methylpyrrolidone, γ -butyrolactone, tetrahydrofuran, dioxane, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, ethyl acetate, butyl acetate, ethyl lactate, toluene, xylene, diethylene glycol dimethyl ether and diethylene glycol dimethyl ether;

10. The method for producing a photosensitive polyimide precursor resin according to claim 9, wherein,

when the fluorine-containing segment is blocked by carboxyl, the photosensitive segment and the silicon-containing segment are blocked by amino;

when the fluorine-containing segment is blocked by amino, the photosensitive segment and the silicon-containing segment are blocked by carboxyl.

11. The method for producing a photosensitive polyimide precursor resin according to claim 9, wherein the photosensitive diamine monomer is 5 to 40% of the total diamine monomer species involved in the synthesis of the precursor resin, the silicon-containing diamine monomer is 5 to 40% of the total diamine monomer species involved in the synthesis of the precursor resin, and the fluorine-containing diamine monomer is 20 to 90% of the total diamine monomer species involved in the synthesis of the precursor resin.

12. A photosensitive resin composition comprising the photosensitive polyimide precursor resin according to any one of claims 1 to 7.