CN114561008A

CN114561008A - Alkali-soluble resin, positive photosensitive resin composition, cured film, and display device

Info

Publication number: CN114561008A
Application number: CN202210208987.0A
Authority: CN
Inventors: 周小明; 王元强; 肖桂林; 鲁丽平; 朱双全
Original assignee: Hubei Dinglong Co ltd; Wuhan Rouxian Technology Co ltd
Current assignee: Hubei Dinglong Co ltd; Wuhan Rouxian Technology Co ltd
Priority date: 2022-03-04
Filing date: 2022-03-04
Publication date: 2022-05-31
Anticipated expiration: 2042-03-04
Also published as: CN114561008B

Abstract

The invention discloses an alkali-soluble resin, a positive photosensitive resin composition, a cured film and a display device, which relate to the technical field of photoelectric display. The alkali soluble resin comprises structure (a1) and structure (a 2); the structure (a1) comprises structural formula (a11) and/or structural formula (a12), and the structure (a2) comprises any one or more of structural formula (a21), (a22) and (a 23);

in the structural formula (a11) and the structural formula (a12), A is an organic group containing at least 6 carbons;

r in the structural formula (a21)₀Represents a C1-4 hydrocarbon group, structureIn formulae (a21), (a22), and (a23), a represents a connecting position. The positive photosensitive resin composition comprising the alkali-soluble resin of the present invention has high exposure sensitivity and excellent image-forming ability.

Description

Alkali-soluble resin, positive photosensitive resin composition, cured film, and display device

Technical Field

The invention relates to the technical field of photoelectric display, in particular to an alkali-soluble resin, a positive photosensitive resin composition, a cured film and a display device.

Background

Polyimide (PI) is an ideal polymer material with excellent heat resistance, mechanical properties, electrical insulation properties and chemical stability, and is commonly used in aerospace, semiconductor, optoelectronics and microelectronics. Compared with common polyimide, the photosensitive polyimide (PSPI) can realize pattern processing without other photoresist, shortens the process route and is an ideal insulating material in the fields of electronics and microelectronics.

In recent years, with the development of miniaturization of semiconductor elements, finer exposure-development sensitivity and image resolution are also required for interlayer insulating films, passivation layers, and the like of semiconductor elements; based on this, in the prior art, a photosensitive polyimide resin composition varnish is often used on the surface of a semiconductor element, and is developed under the condition of alkali liquor after exposure, so that an ideal pattern can be obtained; however, this tends to require high exposure sensitivity and development resolution of the photosensitive polyimide resin composition.

Conventionally, a positive photosensitive resin composition is known, which is a composition of a soluble resin such as polyamic acid, polyamic acid/polyimide, polyamic acid ester/polyamic acid/polyimide, etc. with a photoacid generator (e.g., naphthoquinone diazide), a thermal crosslinking agent, and a solvent. In the case of polyamic acid, the polyamic acid has a relatively high solubility in an alkali solution, and the addition of a photoacid generator naphthoquinone diazide can make the photosensitive resin composition resistant to alkali to some extent, but the resolution of an image after exposure is low, and the pattern is not desirable. Therefore, in order to adjust the alkali solubility of polyamic acid, a polyamic acid/polyimide resin composition has been developed. However, since the ratio of polyimide in the polyamic acid/polyimide, polyamic acid ester/polyamic acid/polyimide resin composition has a close relationship with solubility and ultraviolet transmittance, and has a large influence on exposure sensitivity and image resolution, too many ester groups may result in slow development (slow dissolution rate), poor contrast, or poor image resolution. In addition, in order to improve the alkali solubility of polyimide, the solubility is often improved by introducing a phenolic hydroxyl group, but a dark film loss is caused.

Therefore, increasing the solubility difference before and after exposure is an urgent problem to be solved to obtain a photosensitive resin composition with high contrast, high resolution and high sensitivity.

Disclosure of Invention

An object of the present invention is to solve the above-described problems and to provide an alkali-soluble resin, a positive photosensitive resin composition, a cured film, and a display device.

The first aspect of the present invention provides an alkali-soluble resin comprising a structure (a1) and a structure (a 2); the structure (a1) comprises structural formula (a11) and/or structural formula (a12), and the structure (a2) comprises any one or more of structural formula (a21), (a22) and (a 23);

r in the structural formula (a21)₀Represents a hydrocarbon group having 1 to 4 carbon atoms, and each of the structural formulae (a21), (a22), and (a23) represents a bonding site.

Preferably, the alkali soluble resin preferably comprises structural formula (a11) and structure (a2), wherein structure (a2) comprises any one or more of structural formula (a21), (a22), (a 23). Such as, technical schemes comprising structural formula (a11) and structural formula (a 21); or, technical schemes comprising structural formula (a11) and structural formula (a 22); or structural formula (a11) and structural formula (a 23).

Further, the proportion of the structural formula (a11) and/or the structural formula (a12) in the alkali-soluble resin is 0.5 mol% to 20 mol%, preferably 0.5 mol% to 15 mol%, more preferably 0.5 mol% to 5 mol%;

the proportion of the structural formula (a21) in the alkali-soluble resin is from 50 mol% to 80 mol%, preferably from 60 mol% to 70 mol%, and the proportion of the structural formula (a22), (a23) in the alkali-soluble resin is from 20 mol% to 40 mol%, preferably from 30 mol% to 40 mol%. The structures (a21), (a22), and (a23) above the highest ratio affect the exposure rate.

Further, the alkali soluble resin structure is structural formula (a3) and/or structural formula (a 4):

in the structural formulas (a3) and (a4), X, Y, Z, W represents a reaction residue of dianhydride, P, Q, R, S represents a reaction residue of diamine, wherein any one or more of P, Q, R, S and K comprises a structural formula (a11) and/or any one or more of structural formulas (a12), P, Q, R, S, X, Y, Z and W takes any one of structural formulas (a21), (a22) and (a23) as a substituent group, and L is₁、L₂Each represents a repeating unit bonded to the left and right, R₁、R₂H or an organic group containing 1 to 8 carbon atoms, a, b, c, d, e, f, g and H are integers of 0 to 4, a + b + c + d > 0, e + f + g + H > 0, and m, n, k and l are integers of 1 to 1000.

Further, a component represented by the following general formula (K1) or (K2) is introduced into the polyimide precursor solution, and after the reaction, a compound having the structural formulae (a21), (a22), and (a23) is introduced;

in the general formula (K1) or (K2), A is an organic group having at least 6 carbons, R₃Is any organic radical, R₄Is a chlorine atom or optionally contains NH₂Organic group of (2)The clusters i1 and i2 represent polymerization degrees, i1 is not less than 1, and i2 is not less than 1.

The diamine for forming the polyimide precursor includes an aliphatic diamine or an aromatic diamine, preferably a diamine containing a hydroxyl group; the dianhydride for forming the polyimide precursor includes an aromatic dianhydride, preferably a dianhydride other than a biphenyl structure.

The polyimide precursor comprises polyamic acid, polyamic acid ester, polyimide and a mixture thereof, and can be changed into polyimide after being treated by high temperature or chemical dehydrating agent.

Preferably, R₄Is a chlorine atom, preferably i1 is 1-4, i2 is 1-4; preferably, R₄Is optionally NH₂The organic group of (2) is added with the component shown in the general formula (K1) or (K2) after the diamine monomer and the dianhydride monomer are polymerized.

Further, in the general formula (K1) or (K2), the functional group-N-O-CO-or-N-O-SO₂The number of-is 2, the molar mass of the formula (K1) or (K2) is less than or equal to 3000, preferably less than or equal to 2000; functional groups-N-O-CO-or-N-O-SO₂The number of-is not less than 3, the molar mass of the compounds of the formula (K1) or (K2) is not more than 50000, preferably not more than 20000.

A second aspect of the present invention provides a positive photosensitive resin composition including the alkali-soluble resin provided by the first aspect of the present invention, the positive photosensitive resin composition comprising:

(a) 100 parts by weight of an alkali-soluble resin;

(b) 10-40 parts of a photoacid generator;

(c) 10-60 parts of thermal cross-linking agent;

(d) an organic solvent.

The third aspect of the present invention provides a cured film obtained by coating, prebaking, exposing, postbaking, developing and curing the positive photosensitive resin composition provided by the second aspect of the present invention.

A fourth aspect of the present invention provides a display device comprising the cured film provided by the third aspect of the present invention.

Compared with the prior art, the invention has the following beneficial effects: the present invention provides a positive photosensitive resin composition having high exposure sensitivity, high contrast and excellent image forming ability by designing the alkali soluble resin containing the structural formulae (a11), (a12) and (a21), (a22), (a23) to further increase the ratio of the dissolution rates of the exposed portion and the unexposed portion.

Detailed Description

The present invention provides an alkali-soluble resin, a positive photosensitive resin composition, a cured film and a display device, and will be described below with reference to specific embodiments. It should be noted that the following examples are illustrative of the present invention, and are not intended to limit the present invention. Other combinations and various modifications within the spirit or scope of the present invention may be made without departing from the spirit or scope of the present invention.

< alkali soluble resin >

in the structural formula (a11) and the structural formula (a12), a is an organic group having at least 6 carbons, specifically an acid dianhydride residue, for example, an organic group having 2 or more carbon atoms, preferably an aromatic ring or an aliphatic ring, and preferably an aromatic ring from the viewpoint of obtaining high thermodynamic properties.

R in the structural formula (a21)₀Represents a hydrocarbon group having 1 to 4 carbon atoms, such as ethyl, propyl, tert-butyl, etc., and denotes a bonding site in the structural formulae (a21), (a22), and (a 23).

In an embodiment of the present invention, the proportion of the structural formula (a11) and/or the structural formula (a12) in the alkali-soluble resin is 0.5 mol% to 20 mol%, preferably 0.5 mol% to 15 mol%, more preferably 0.5 mol% to 5 mol%. Less than 0.5 mol%, the ratio of the dissolution rates of the exposed portion and the unexposed portion cannot be increased; above 20 mol%, the mechanical properties, thermal properties, etc. of the resin composition itself are affected.

The proportion of the formula (a21) in the alkali-soluble resin is from 50 mol% to 80 mol%, preferably from 60 mol% to 70 mol%; the proportion of structural formulae (a22), (a23) in the alkali-soluble resin is from 20 mol% to 40 mol%, preferably from 30 mol% to 40 mol%. The ratios of structural formulae (a21), (a22), (a23) are too low to achieve the effect of increasing the ratio of the dissolution rates of the exposed portion and the unexposed portion; the ratios of the structural formulae (a21), (a22), and (a23) are too high, which adversely affects the dissolution rate of the exposed portion.

Preferably, the alkali soluble resin preferably includes structural formula (a11) and structural formula (a2) from the viewpoint of increasing the dissolution rate of exposed portions. Such as, technical schemes comprising structural formula (a11) and structural formula (a 21); or, technical schemes comprising structural formula (a11) and structural formula (a 22); or structural formula (a11) and structural formula (a 23).

In an embodiment of the present invention, the structural formula (a11) and/or the structural formula (a12) is or is not on the main chain of the alkali soluble resin. The grafting of formulae (a21), (a22), (a23) onto the backbone of the alkali-soluble resin is now described with respect to the introduction of formulae (a11) or (a12), respectively, and the grafting of formulae (a21), (a22), (a 23):

for embodiments in which the structural formula (a11) and/or structural formula (a12) is on the alkali soluble resin backbone, it is preferably not at the end of the alkali soluble resin backbone; alternatively, it is preferable that the structural formula (a11) and/or the structural formula (a12) is not in the main chain of the alkali-soluble resin.

Further, for the technical solution of structural formula (a11) and/or structural formula (a12) on the main chain of the alkali-soluble resin, the alkali-soluble resin structure is as shown in the following structural formula (a 3):

in the structural formula (a3), X, Y represents a reaction residue of dianhydride, P, Q represents a reaction residue of diamine, wherein P and/or Q contains any one or more of structural formula (a11) or structural formula (a12), P, Q, X and Y, and any one of structural formula (a21), (a22) and (a23) is used as a substituent group, R₁H or an organic group containing 1-8 carbon atoms, a, b, c and d are integers of 0-4, a + b + c + d is not less than 0, and m and n are integers of 1-1000, such as 1, 10, 100, 200, 500, 900.

Specifically, the technical scheme is realized by taking the diamine derivative containing the structural formula (a11) or the structural formula (a12) as a raw material, wherein the compound is represented by the following general formula (K1) or (K2), and the proportion of the diamine derivative containing the structural formula (a11) or the structural formula (a12) in the alkali-soluble resin is 0.5 mol% to 20 mol%, preferably 0.5 mol% to 15 mol%, and more preferably 0.5 mol% to 5 mol%. For polyimide resins, it is understood that the proportion of the diamine derivative of formula (a11) or formula (a12) in the sum of the diamine and dianhydride molar ratios is from 0.5 mol% to 20 mol%, preferably from 0.5 mol% to 15 mol%, more preferably from 0.5 mol% to 5 mol%.

In the general formula (K1) or (K2), a is an acid dianhydride residue, for example, an organic group having 2 or more carbon atoms, and preferably contains an aromatic ring or an aliphatic ring. R₃Is any organic group, preferably an aromatic group, such as phenyl, biphenyl, naphthyl, substituted groups thereof and the like. R₄Is optionally NH₂An organic group of (a); i1 and i2 represent polymerization degrees, i1 is not less than 1, and i2 is not less than 1.

For the adding time of the diamine derivative, the diamine derivative containing the structural formula (a11) or the structural formula (a12) and a diamine monomer are added together, or the diamine monomer and a dianhydride monomer react and then are added; the diamine monomer and the dianhydride monomer are reacted at normal temperature after the dianhydride and the diamine are mixed. From the viewpoint of not impairing the mechanical and thermal properties of the cured resin pattern, it is preferable that the diamine monomer is added after reacting with the dianhydride monomer; from the viewpoint of obtaining a proper slurry concentration, the reaction ratio of the diamine monomer and the dianhydride monomer is such that the weight average molecular weight of the polymer after the reaction of the diamine monomer and the dianhydride monomer is 70000-100000. In this preferred embodiment, the partial formula (a11) or formula (a12) is located at or near the ends of the polymer backbone and the partial formula (a11) or formula (a12) is located in the middle of the backbone.

Wherein the diamine derivative of the structural formula (a11) or the structural formula (a12) contains a functional group of-N-O-CO-or-N-O-SO₂The number of-is preferably 2, and the molar mass of the diamine derivative is less than or equal to 3000, preferably less than or equal to 2000. If the molar mass of the monomer is too large or the functional group-N-O-CO-or-N-O-SO₂Too many of-functional groups-N-O-CO-or-N-O-SO₂Too long chain segments in the main chain of the polyimide resin can lead to a large amount of chain segment breakage after exposure, which can cause too high outgassing and further affect the film-forming quality.

In the general formula (K1), R₃Is phenyl, R₄is-NH-BP-NH₂For example, wherein BP represents a phenol group, a diamine derivative containing the structural formula (a11) was synthesized by the following scheme (1):

in the general formula (K2), R₃Is phenyl, R₄is-NH-BP-NH₂For example, where BP represents a phenol group, the synthetic route for diamine derivatives containing the structural formula (a12) is: the above-mentioned m-benzenedisulfonyl chloride in the above-mentioned route (1) is replaced with m-dibenzoyl chloride, and other conditions are not changed, specifically, the following route (2):

further, the following diamine derivatives containing the structural formula (a11) or the structural formula (a12) can be exemplified:

for embodiments in which structural formula (a11) and/or structural formula (a12) are not in the backbone of the alkali soluble resin, it is preferred that the alkali soluble resin represented by structural formula (a4) be formed.

In the structural formula (a4), X, Y, Z, W represents a reaction residue of a dianhydride monomer, P, Q, R, S represents a reaction residue of a diamine monomer, K represents a compound containing the structural formula (a11) or the structural formula (a12), any one or more of P, Q, R, S, X, Y, Z and W has any one of the structural formulae (a21), (a22) and (a23) as a substituent, and L₁、L₂Each represents a repeating unit, R₁、R₂H or an organic group containing 1 to 8 carbon atoms, a, b, c, d, e, f, g and H are integers of 0 to 4, a + b + c + d > 0, e + f + g + H > 0, and m, n, k and l are integers of 1 to 1000.

Specifically, the technical scheme is realized by taking the acyl chloride derivative containing the structural formula (a11) or the structural formula (a12) as shown in the following general formula (K1) or (K2) as a raw material, wherein the proportion of the structural formula (a1) and/or the structural formula (a2) in the alkali-soluble resin is 0.5 mol% to 20 mol%, preferably 0.5 mol% to 15 mol%, and more preferably 0.5 mol% to 5 mol%.

In the general formula (K1) or (K2), a is an acid dianhydride residue, for example, an organic group having 2 or more carbon atoms, and preferably contains an aromatic ring or an aliphatic ring. R₃Is any organic group, preferably an aromatic group such as phenyl, biphenyl, naphthyl, a substituent thereof, and the like. R₄Is a chlorine atom; i1 and i2 represent polymerization degrees, i1 is not less than 1, and i2 is not less than 1. Specifically, sulfonyl chloride groups or formyl chloride groups at two ends of (K1) or (K2) react with hydroxyl at any position on a resin main chain repeating unit to enable two groups to be the same or differentAre connected with the polymer chain segment.

For the timing of addition of the acid chloride derivative, (K1) or (K2) is added after the addition of the capping agent after the polymerization of the diamine monomer and the dianhydride monomer. The specific operation is as follows: mixing diamine and dianhydride, reacting at normal temperature, adding a blocking agent, and continuing to react; after cooling to 0 deg.C, the acid chloride derivative (K1) or (K2) is added to react to obtain the alkali-soluble resin, such as the following structural formulas (a4-1) and (a 4-2):

the acid chloride derivative may react with a hydroxyl group at any position of the main chain, and the connection mode represented by the structural formula (a4-1) and (a4-2) is not intended to limit the present invention.

As a preferred embodiment, the functional group-N-O-CO-or-N-O-SO-in the acid chloride derivative₂The number of-is 2, the molar mass of the formula (K1) or (K2) is less than or equal to 3000, preferably less than or equal to 2000; functional groups-N-O-CO-or-N-O-SO₂The number of-is not less than 3, such as 4, 6, 8, etc., the molar mass of the compounds of the formula (K1) or (K2) is not more than 50000, preferably not more than 20000. For further clarification, the hydroxyl-containing monomer is used as raw material to synthesize alkali soluble resin, (K1) or (K2) both ends of which have groups capable of reacting with hydroxyl on the resin main chain, such as acyl chloride group, including-SO₂Cl or-COCl; compound K reacts with hydroxyl groups to form a bridged structure.

Wherein, with R₃For the phenyl example, the acid chloride derivative (K1) or (K2) is synthesized by the following scheme (3) or scheme (4):

route (3) or route (4) controls the degree of polymerization by adjusting the raw material ratio, wherein i3 and i4 represent the degree of polymerization, i3 is not less than 1, i4 is not less than 1, and the molar mass of the acid chloride derivative (K1) or (K2) is not more than 50000, preferably not more than 20000.

For such a technical scheme, the following acid chloride derivatives (K1) or (K2) can be exemplified:

in the above formula, w and h represent polymerization degrees and are integers of not less than 1.

With respect to the incorporation of the structural formulae (a21), (a22), (a23) in the embodiment of the present invention, it is now illustrated that the diamines and dianhydrides used in the following examples of the incorporation of the structural formulae (a21), (a22), (a23), respectively, are merely examples and are not intended to be limiting.

Structural formula (a21) is obtained by reacting an esterifying reagent, including but not limited to N, N-dimethylformamide di-tert-butyl acetal, alcohols, and the like, with the carboxyl group on the polyamic acid dianhydride residue. The specific method for utilizing the N, N-dimethylformamide di-tert-butyl acetal comprises the following steps:

diamine and dianhydride were dissolved in a solvent in NMP (100g) under a stream of dry nitrogen, reacted at 25 ℃ for 4 to 16 hours, then added with N, N-dimethylformamide di-tert-butyl acetal, and reacted at room temperature for 2 to 8 hours. Examples of the following synthetic routes can be mentioned:

the introduction method of the structural formula (a22) is as follows: diamine and dianhydride were dissolved in a solvent in NMP (100g) under a dry nitrogen flow, reacted at 25 ℃ for 4 to 16 hours, added with di-t-butyl dicarbonate, catalyst diethylmethylamine and solvent cyclohexanone, and reacted at room temperature for 2 to 8 hours. Examples of the following synthetic routes can be mentioned:

the introduction method of the structural formula (a23) is as follows: dissolving diamine and dianhydride in a solvent in NMP (100g) under a dry nitrogen flow, reacting at 25 ℃ for 4-16H, adding 3, 4-dihydro-2H-pyran, p-toluenesulfonic acid and THF solvent, and reacting at room temperature for 2-8H. Examples of the following synthetic routes can be mentioned:

in the embodiment of the present invention, based on the above structural formula (a4), alkali-soluble resins containing structural formula (a11) or structural formula (a12) and containing any one of structural formulae (a21), (a22), and (a23) are exemplified, but not limited thereto. X, Y, Z, W, P, Q, R, S, R in the following example₁、R₃And the lower corner marks involved in the examples are the same as described above and will not be described further herein.

In structural formula (a3) and structural formula (a4), other dianhydride monomers such as aromatic dianhydride, alicyclic dianhydride, hydroxyl group-containing dianhydride, etc. are not limited except for the dianhydride monomers used for synthesizing the dianhydride monomer containing structural formula (a11), structural formula (a12), (a21), (a22), (a 23). Examples thereof include pyromellitic dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 2,3,5, 6-pyridinetetracarboxylic dianhydride, bicyclo [3.1.1] hept-2-ene tetracarboxylic dianhydride, 3,3 ', 4,4' -biphenyltetracarboxylic dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 3,4,9, 10-perylenetetracarboxylic dianhydride, bicyclo [2.2.2] octane tetracarboxylic dianhydride, 2,3,3 ', 4' -biphenyltetracarboxylic dianhydride, bis (3, 4-dicarboxyphenyl) methane dianhydride, adamantane tetracarboxylic dianhydride, 2 ', 3, 3' -biphenyltetracarboxylic dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, cyclobutane tetracarboxylic dianhydride, 3,3 ', 4,4' -benzophenonetetracarboxylic dianhydride, and the like, Other aromatic dianhydrides or aliphatic dianhydrides such as bis (3, 4-dicarboxyphenyl) sulfone dianhydride, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 2 ', 3, 3' -benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4' -diphenyl ether tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,2,5, 6-naphthalene tetracarboxylic dianhydride, bicyclo [2.2.1] heptane tetracarboxylic dianhydride, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) hexafluoropropane dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, and bicyclo [3.3.1] tetracarboxylic dianhydride, or the following hydroxyl-containing dianhydrides:

these dianhydrides may be used alone or in combination of two or more.

In the structural formula (a3) and the structural formula (a4), the diamine monomers other than the diamine monomers used for synthesizing the compound containing the structural formula (a11), the structural formula (a12), (a21), (a22) and (a23) are not limited at all, and may be one or more of aromatic diamine, fluorine-containing diamine, siloxane-containing structure and hydroxyl-containing diamine. From the viewpoint of improving alkali solubility and facilitating introduction of the structural formula (a11) or the structural formula (a12), it is preferable to use a hydroxyl group-containing diamine monomer in combination with other diamine monomers, and among them, the hydroxyl group-containing diamine monomer can be exemplified as follows:

examples of the aromatic diamine include: m-phenylenediamine, p-phenylenediamine, 1, 5-naphthalenediamine, 2, 6-naphthalenediamine, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) biphenyl, bis (3-amino-4-hydroxyphenyl) fluorene, 1, 4-bis (4-aminophenoxy) benzene, 2 '-dimethyl-4, 4' -diaminobiphenyl, 2 '-diethyl-4, 4' -diaminobiphenyl, 2, 6-naphthalenediamine, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) fluorene, 3,3 '-dimethyl-4, 4' -diaminobiphenyl, 3,3 '-diethyl-4, 4' -diaminobiphenyl, 2 ', 3, 3' -tetramethyl-4, 4 '-diaminobiphenyl, 3, 3', 4,4 '-tetramethyl-4, 4' -diaminobiphenyl, 2 '-bis (trifluoromethyl) -5, 5' -dihydroxybenzidine, 3,4 '-diaminodiphenyl ether, 3, 4' -diaminodiphenylmethane, 4,4 '-diaminodiphenylmethane, 3, 4' -diaminodiphenylsulfone, 4,4 '-diaminodiphenylsulfone, 3, 4' -diaminodiphenylsulfide, sulfur oxide, and combinations thereof, One or more diamines such as 4,4' -diaminodiphenyl sulfide, 1, 4-bis (4-aminophenoxy) benzene, 4' -diaminodiphenyl ether, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl } ether, 3, 5-diaminobenzoic acid, and 3-carboxy-4, 4' -diaminodiphenyl ether.

Examples of the fluorine-containing diamine include the following structures:

it should be noted that, introducing fluorine atoms may reduce the adhesion of the resin composition to the substrate to some extent, and in order to reduce this adverse effect and improve the adhesion of the resin composition to the substrate, the diamines in the structural formula (a3) and the structural formula (a4) further include diamines having a siloxane structure, wherein the molar percentage of the diamines having a siloxane structure in the structural formula (a3) and the structural formula (a4) is 0 to 10 mol% on the basis of not reducing the heat resistance; examples may be cited: diamines such as 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane (SiDA) and bis (p-aminophenyl) octamethylpentasiloxane (SiDA), and 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane (SiDA) is preferable.

In order to better regulate the molecular weight of the resin provided by the second aspect of the present invention, a certain end-capping agent may be added during polymerization, and specific examples thereof may be, but are not limited to, one or more combinations of the following exemplified compounds: monofunctional aromatic amine: 3-aminophenol, 2-aminophenol, 4-aminophenol, 3-aminobenzoic acid, 3-amino-o-methylbenzoic acid, 3-amino-m-methylbenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 1-amino-8-hydroxynaphthalene, 1-amino-7-hydroxynaphthalene, 1-amino-6-hydroxynaphthalene, 1-amino-5-hydroxynaphthalene, 1-amino-4-hydroxynaphthalene, 1-amino-3-hydroxynaphthalene, 1-amino-2-hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 3-aminobenzoic acid, 3-amino-methylbenzoic acid, 3-amino-m-methylbenzoic acid, 4-aminosalicylic acid, 5-amino-5-hydroxynaphthalene, 1-amino-4-hydroxynaphthalene, 1-amino-3-hydroxynaphthalene, 1-amino-2-hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, a, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy-2-aminonaphthalene, 3-amino-4, 6-dihydroxypyrimidine, 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline. Monofunctional aromatic anhydrides: maleic anhydride, phthalic anhydride, cyclohexane dicarboxylic anhydride, and cyclohexane dicarboxylic anhydride. Monofunctional aromatic acid: benzoic acid, o-methylbenzoic acid, m-methylbenzoic acid, p-methylbenzoic acid, 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, carboxynaphthalene, 2-hydroxy-naphthoic acid, 3-hydroxy-naphthoic acid, 4-hydroxy-naphthoic acid, 5-hydroxy-naphthoic acid, 6-hydroxy-naphthoic acid, 7-hydroxy-naphthoic acid, 8-hydroxy-naphthoic acid, 9-hydroxy-naphthoic acid.

The end-capping agent is introduced in a proportion of 0.005 to 0.5, further 0.01 to 0.4, based on the total molar amount of all the diamine monomers and dianhydride monomers; when the content is within the above range, a resin composition having an appropriate solution viscosity and excellent film properties can be obtained.

< Positive photosensitive resin composition >

A second aspect of the present invention provides a positive photosensitive resin composition comprising the alkali-soluble resin provided by the first aspect of the present invention, a photoacid generator, a thermal crosslinking agent, and an organic solvent.

Examples of the photoacid generator in the positive photosensitive resin composition include: one or more of quinone diazide compounds (naphthoquinone diazide sulfonate compounds), sulfonium salts, phosphonium salts, diazonium salts, iodonium salts, and the like; these quinonediazide compounds can be synthesized by esterification of a phenolic hydroxyl compound with quinonediazidosulfonyl chloride. In the present invention, as the quinonediazide compound, a compound in which a 5-naphthoquinonediazide sulfonyl group or a 4-naphthoquinonediazide sulfonyl group is bonded to a compound having a phenolic hydroxyl group is preferably used. The phenolic hydroxy compound includes the following examples:

as the quinonediazide compound, any one or a combination of plural kinds of naphthoquinonediazidosulfonate structures are preferably used in the molecular structure. Specific examples thereof include the following commercial photoacid generators PAC-1 to PAC-20, and the following may be used in any one or a combination of plural kinds.

The amount of the photoacid generator added is 5 to 40 parts by weight, preferably 10 to 30 parts by weight, with respect to 100 parts by weight of the alkali-soluble resin.

As for the thermal crosslinking agent in the photosensitive resin composition, the thermal crosslinking agent is crosslinked with the alkali-soluble resin provided in the first aspect of the present invention by heating, thereby improving the chemical resistance of the cured film. The thermal crosslinking agent in the invention is selected from one or more of epoxy compound and alkoxy/hydroxymethyl compound.

Among them, the Epoxy compound is preferably a compound having two or more Epoxy groups in one molecule, and examples thereof include, for example, bisphenol a type Epoxy resins, bisphenol a type oxetane resins, bisphenol F type Epoxy resins, bisphenol F type oxetane resins, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Epoxy group-containing silicones such as polymethyl (glycidyloxypropyl) siloxane, and the like, but are not limited thereto, and specifically, there are, for example, EPICLON, series products such as EXA, Yuka Shell Epoxy co. Examples may be mentioned: the Dainippon ink chemical industry EPICLON, EXA series products such as EPICLON850-S, EPICLONHP-4032, EPICLON HP-7200, EPICLON HP-820, EPICLON HP-4700, EPICLON EXA-4710, EPICLON HP-4770, EPICLON EXA-4816, EPICLON EXA-4822, and the like, and the ADEKA company EP series products such as EP 4003S, EP-4000S, and the like.

The alkoxy/hydroxymethyl compound is preferably a compound having 2 to 8 or more alkoxy and/or hydroxymethyl functional groups in one molecule, and is, for example, a phenol compound such as (2-hydroxy-5-methyl) -1, 3-benzenedimethanol or 2,2 ', 6, 6' -tetramethoxymethyl bisphenol A. There may be mentioned the trade names DML, TriML, DMOM, HMOM, TMOM etc. series of the state chemistry, such as DML-PC, DML-PEP, DML-OC, DML-OEP, DMOM-PC, DMOM-PTBP etc., and the MX, MW series of the three-and chemistry, such as MX-270, MW-100LM etc.

The addition amount of the thermal crosslinking agent of the present invention is 10 to 60 parts by weight, preferably 20 to 50 parts by weight, compared to 100 parts by weight of the alkali-soluble resin.

As the organic solvent in the photosensitive resin composition, the following examples are included, but not limited to: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, propyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl lactate, bis (2-methoxyethyl) ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, methyl ethyl ketone, cyclohexanone, cyclopentanone, butanol, isobutanol, pentanol, γ -butyrolactone, N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and the like.

In addition, a thermal acid generator may be used in the photosensitive resin composition of the present invention within a range not impairing the effects of the present invention.

Specific examples of the preferable thermal acid generator include SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-60L, SI-80L, SI-100L, SI-110L, SI-145L, SI-150L, SI-160L, SI-180L (all manufactured by shin-chan chemical industry Co., Ltd.), 4-hydroxyphenyl dimethylsulfonium, benzyl-4-hydroxyphenyl methylthioninium, 2-methylbenzyl-4-acetylphenyl methylthioninium, 2-methylbenzyl-4-benzoyloxyphenyl methylthioninium, their methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, p-toluenesulfonate. More preferably 4-hydroxyphenyl dimethylsulfonium, benzyl-4-hydroxyphenyl methylthioninium, 2-methylbenzyl-4-acetylphenyl methylthioninium, 2-methylbenzyl-4-benzoyloxyphenyl methylthioninium, their methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, p-toluenesulfonate. The above-mentioned compounds may be used alone or in combination of 2 or more.

The amount of the thermal acid generator is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the alkali-soluble resin. When the amount is less than 0.01 part by weight, the function of the crosslinking accelerator is not sufficiently exhibited to form a film having low hardness, and when the amount is more than 10 parts by weight, the sensitivity is lowered, or the mechanical or electrical properties of the cured film are deteriorated.

< cured film >

The third aspect of the present invention provides a cured film obtained from the positive photosensitive resin composition provided by the second aspect of the present invention, specifically, by the steps of coating, prebaking, exposing, postbaking, developing, and curing.

The coating step is a step of coating the positive photosensitive resin composition on the substrate, and examples of the coating method include spin coating, spray coating, blade coating, screen coating, slit coating, and the like. Preferably, the film thickness after drying is 0.5-50 μm, and drying is carried out by oven, hot plate, infrared oven, etc. at 40-80 deg.C for 1-10 min or stage temperature programmed drying treatment to volatilize organic solvent. Examples of the substrate include, but are not limited to, silicon wafers, ceramics, gallium arsenic, organic circuit boards, inorganic circuit boards, and substrates on which constituent materials of circuits are disposed.

A pre-drying step, wherein the pre-drying temperature is 70-130 ℃, such as 70-100 ℃ or 100-130 ℃. The pre-drying time is 1-5 min.

An exposure step of applying and drying a positive photosensitive resin composition film formed on a substrate, and exposing the film by irradiating exposure light with a mask having a desired pattern; the exposure light source is preferably a mercury lamp emitting i (365nm), h (405nm), g (436nm) rays; as the exposure apparatus, a reduction projection type exposure apparatus, a mask aligner, a mirror projection type exposure apparatus, or the like is used.

A post-drying step, wherein the post-drying temperature is 70-130 ℃, such as 70-110 ℃ or 110-130 ℃; preferably 110 ℃; the post-drying time is 1-3 min, such as 1-2 min or 2-3 min; preferably for 2 min.

For the development step, specifically, the exposed portion on the film is removed using a developer. The developer is preferably an aqueous solution of an alkaline compound such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, dimethylamine, dimethylaminoethanol, cyclohexylamine, ethylenediamine, etc.; in addition, one or more of organic solvents such as N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, methanol, ethanol, isopropanol, ethyl lactate, cyclopentanone, cyclohexanone, and acetone are added to these alkaline aqueous solutions.

The developing mode is selected from one of spray developing, dipping developing and ultrasonic dipping developing methods; the conditions such as development time, development temperature, and development step may be conditions under which the exposed portion is removed; after the development, the developed film is preferably rinsed with water, and more preferably rinsed with an aqueous solution of an alcohol or ester of ethanol, isopropanol, or ethyl lactate; before developing, if the film needs to be baked, baking at 50-150 ℃, preferably 50-120 ℃ for 5 s-60 min; after rinsing, the coating is dried by heating at 50 to 200 ℃ for 1 to 60 minutes.

In the curing step, the curing temperature is 230-270 ℃, such as 250 ℃; the curing time is 1 h. The patterned cured film can be obtained by curing.

The cured film having a desired pattern formed from the positive photosensitive resin composition of the present invention can be used for a surface protective film of a semiconductor device, an interlayer insulating film, an insulating layer of an organic Electroluminescence (EL) device, an insulating layer of a Thin Film Transistor (TFT), and the like, but is not limited thereto.

< display device >

A display device according to a fourth aspect of the present invention includes the cured film provided by the third aspect of the present invention. Further, the display device includes, but is not limited to, OLED, TFT-LCD, and the like flexible displays. The cured film is applied to an insulating layer, a pixel defining layer and a planarization layer of a flexible display, or/and a surface protective layer and an insulating layer of a semiconductor device.

Examples

The above and other advantages of the present invention will be better understood by the following examples, which are not intended to limit the scope of the present invention.

Description of abbreviations:

ODA: 4,4' -diaminodiphenyl ether

6 FAP: 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane

SiDA: 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane

6 FODA: 2,2 '-bis (trifluoromethyl) -4, 4' -diaminodiphenyl ether

6 FDA: 2, 2' -bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride

ODPA: 3,3 ', 4,4' -Diphenyl Ether Tetraformic dianhydride

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

CBDA: cyclobutanetetracarboxylic dianhydride

Synthesis example 1

Synthesis of 6FDA diamine derivative A1

Dissolving 0.1mol of 2-amino-4-nitrophenol in 50ml of acetone and 0.34mol of propylene oxide, cooling to-15 ℃, slowly dropwise adding the A3 solution (0.048mol, dissolved in 150ml of propylene glycol monomethyl ether) synthesized in the synthesis example 3, continuously reacting for 4h at-15 ℃ after dropwise adding, then heating to room temperature, filtering, washing a filter cake for a plurality of times by using acetone, and drying for 10h in vacuum at 50 ℃ to obtain the nitro intermediate.

Dissolving the nitro compound in 100ml of NMP, adding 3g of 5% palladium-carbon, introducing hydrogen into an autoclave, continuously stirring at room temperature for 6h, then filtering the reaction liquid to remove the catalyst, pouring the filtrate into water, precipitating a solid product, filtering, and drying in vacuum at 50 ℃ for 24h to obtain the diamine derivative A1 of 6 FDA.

Synthesis example 2

Synthesis of 6FDA diamine derivative A2

The only difference from synthesis example 1 is: starting material A3 was substituted for a4 synthesized in synthesis example 4 under otherwise unchanged conditions to obtain 6FDA diamine derivative a 2.

Synthesis example 3

Synthesis of benzenesulfonyl chloride derivative A3 from 6FDA

10ml of acetone, 0.024mol of propylene oxide and 0.024mol of m-benzenedisulfonyl chloride are added into a three-neck flask, then a mixed solution of 0.01mol of 6FDA hydroxyimide solution (the synthetic method of hydroxyimide is shown in U.S. Pat. No. 6,000,57) and 30ml of acetone is slowly dropped (the temperature of the three-neck flask is kept between minus 5 ℃ and 0 ℃), after dropping, the temperature is slowly raised to room temperature, stirring is carried out for 4 hours, and yellow precipitate is obtained and filtered. The filter cake was washed with dry acetone and dried under vacuum at 50 ℃ for 10h to give A3.

Synthesis example 4

Synthesis of benzoyl chloride derivative A4 of 6FDA

The m-benzenedisulfonyl chloride in synthesis example 3 was replaced with m-phthaloyl chloride, and the other conditions were unchanged.

Synthesis example 5

Synthesis of benzenesulfonyl chloride derivative A5 from 6FDA

30ml of acetone, 0.030mol of propylene oxide and 0.015mol of m-benzenedisulfonyl chloride are added into a three-neck flask, then a mixed solution of 0.01mol of a 6FDA hydroxyimide solution (the synthetic method of hydroxyimide is shown in U.S. Pat. No. 5,000,57) and 5ml of gamma butyrolactone is slowly dripped (the three-neck flask is kept at-5 ℃ to 0 ℃), after dripping, the temperature is slowly raised to room temperature and stirring is carried out for 4 hours, yellow precipitates are obtained, filtering is carried out, filter cakes are washed by dry acetone, and vacuum drying is carried out at 50 ℃ for 10 hours, so that 6FDA benzenesulfonyl chloride derivative A5 is obtained.

Synthesis example 66 Synthesis of benzoyl chloride derivative A6 of FDA

30ml of acetone, 0.030mol of propylene oxide and 0.017mol of isophthaloyl dichloride are added into a three-neck flask, then a mixed solution of 0.01mol of 6FDA hydroxyimide solution (the synthetic method of hydroxyimide is shown in US7374857) and 5ml of gamma butyrolactone is slowly dripped (the three-neck flask is kept between minus 5 ℃ and 0 ℃), after dripping is finished, the temperature is slowly raised to room temperature, stirring is carried out for 4 hours, yellow precipitate is obtained, filtering is carried out, a filter cake is washed by dry acetone, and vacuum drying is carried out for 10 hours at 50 ℃ to obtain the benzoyl chloride derivative A6 of 6 FDA.

< preparation of alkali-soluble resin >

Preparation example 1: synthesis of alkali-soluble resin P1

Bis (4-aminophenyl) hexafluoropropane (0.018mol), 6FAP (0.018mol) and SiDA (0.002mol) were dissolved in NMP (100g) under a stream of dry nitrogen. Subsequently, 6FDA (0.020mol), CBDA (0.020mol) and 40g of NMP were added thereto, and reacted at 25 ℃ for 2 hours. Then 3-aminophenol (0.0024mol) is added to react for 48h at 25 ℃, then the temperature is reduced to 0 ℃, and 0.0042mol of propylene oxide and 0.004mol of A3 are added to react for 4h at 0 ℃. Then the temperature is raised to the room temperature, 0.020mol of N, N-dimethylformamide di-tert-butyl acetal is added, and the temperature is raised to 80 ℃ for reaction for 4 hours. After the reaction is finished, cooling to room temperature, and reacting in 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, the precipitate was filtered, and the filter cake was washed with ethanol: washing with water at a volume ratio of 1:3 for several times, and vacuum-drying the filter cake at 50 ℃ for 72h to obtain a powder of the alkali-soluble resin P1.

Preparation example 2: synthesis of alkali-soluble resin P2

ODA (0.018mol), 6FAP (0.018mol) and SiDA (0.002mol) were dissolved in NMP (100g) under a stream of dry nitrogen. ODPA (0.020mol), CBDA (0.020mol) and 40g of NMP were then added thereto, and reacted at 25 ℃ for 2 hours. Then 3-aminophenol (0.0024mol) is added to react for 48h at 25 ℃, then the temperature is reduced to 0 ℃, 0.0042mol of propylene oxide and 0.004mol of A5 are added to react for 4h at 0 ℃. Then the temperature is raised to the room temperature, 0.025mol of N, N-dimethylformamide di-tert-butyl acetal is added, and the temperature is raised to 80 ℃ for reaction for 4 hours. After the reaction is finished, cooling to room temperature, and adding 2L of ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a volume ratio of 1:3 for several times, and vacuum-drying the filter cake at 50 ℃ for 72h to obtain a powder of the alkali-soluble resin P2.

Preparation example 3: synthesis of alkali-soluble resin P3

6FODA (0.018mol), 6FAP (0.018mol) and SiDA (0.002mol) were dissolved in NMP (100g) under a stream of dry nitrogen. Then, ODPA (0.020mol), BTDA (0.020mol), and 40g of NMP were added thereto, and reacted at 25 ℃ for 2 hours. Then 3-aminophenol (0.0024mol) is added to react for 48h at 25 ℃, then the temperature is reduced to 0 ℃, 0.0042mol of propylene oxide and 0.004mol of A3 are added to react for 4h at 0 ℃. Then the temperature is raised to the room temperature, 0.030mol of N, N-dimethylformamide di-tert-butyl acetal is added, and the temperature is raised to 80 ℃ for reaction for 4 hours. After the reaction is finished, cooling to room temperature, and reacting in 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, the precipitate was filtered, and the filter cake was washed with ethanol: washing with water at a ratio of 1:3 (volume ratio) for several times, and vacuum-drying the filter cake at 50 ℃ for 72h to obtain a powder of the alkali-soluble resin P3.

Preparation example 4: synthesis of alkali-soluble resin P4

Bis (4-aminophenyl) hexafluoropropane (0.018mol), 6FAP (0.018mol) and SiDA (0.002mol) were dissolved in NMP (100g) under a dry nitrogen stream. BTDA (0.020mol), CBDA (0.020mol) and 40g of NMP were then added thereto, and reacted at 25 ℃ for 2 hours. Then 3-aminophenol (0.0024mol) is added to react for 48h at 25 ℃, then the temperature is reduced to 0 ℃, 0.0042mol of propylene oxide and 0.004mol of A5 are added to react for 4h at 0 ℃. Finally, the temperature is raised to the room temperature, 0.0036mol of di-tert-butyl dicarbonate and 0.004mol of catalyst diethyl methylamine are added for reaction for 8 hours. After the reaction was complete, the reaction was quenched in 2L of ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a volume ratio of 1:3 for several times, and vacuum-drying the filter cake at 50 ℃ for 72h to obtain a powder of the alkali-soluble resin P4.

Preparation example 5: synthesis of alkali-soluble resin P5

ODA (0.018mol), 6FAP (0.018mol) and SiDA (0.002mol) were dissolved in NMP (100g) under a stream of dry nitrogen. Then, ODPA (0.020mol), 6FDA (0.020mol), and 40g of NMP were added thereto, and the reaction was carried out at 25 ℃ for 2 hours. Then 3-aminophenol (0.0024mol) is added to react for 48h at 25 ℃, then the temperature is reduced to 0 ℃, 0.0042mol of propylene oxide and 0.004mol of A3 are added to react for 4h at 0 ℃. Finally, the temperature is raised to the room temperature, 0.0054mol of di-tert-butyl dicarbonate and 0.006mol of catalyst diethyl methylamine are added for reaction for 8 hours. After the reaction was complete, the reaction was carried out in 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, the precipitate was filtered, and the filter cake was washed with ethanol: washing with water at a ratio of 1:3 (volume ratio) for several times, and vacuum-drying the filter cake at 50 ℃ for 72h to obtain a powder of the alkali-soluble resin P5.

Preparation example 6: synthesis of alkali-soluble resin P6

6FODA (0.018mol), 6FAP (0.018mol) and SiDA (0.002mol) were dissolved in NMP (100g) under a stream of dry nitrogen. ODPA (0.020mol), CBDA (0.020mol) and 40g of NMP were then added thereto, and reacted at 25 ℃ for 2 hours. Then 3-aminophenol (0.0024mol) is added to react for 48h at 25 ℃, then the temperature is reduced to 0 ℃, 0.0042mol of propylene oxide and 0.004mol of A3 are added to react for 4h at 0 ℃. Finally, the temperature is raised to the room temperature, 0.0072mol of di-tert-butyl dicarbonate and 0.008mol of catalyst diethyl methylamine are added for reaction for 8 hours. After the reaction was complete, the reaction was carried out in 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, the precipitate was filtered, and the filter cake was washed with ethanol: washing with water at a volume ratio of 1:3 for several times, and vacuum-drying the filter cake at 50 ℃ for 72h to obtain a powder of the alkali-soluble resin P6.

Preparation example 7: synthesis of alkali-soluble resin P7

Bis (4-aminophenyl) hexafluoropropane (0.018mol), 6FAP (0.018mol) and SiDA (0.002mol) were dissolved in NMP (100g) under a stream of dry nitrogen. ODPA (0.020mol), CBDA (0.020mol) and 40g of NMP were then added thereto, and reacted at 25 ℃ for 2 hours. Then 3-aminophenol (0.0024mol) is added to react for 48h at 25 ℃, then the temperature is reduced to 0 ℃, 0.0042mol of propylene oxide and 0.004mol of A3 are added to react for 4h at 0 ℃. Finally, the temperature is raised to the room temperature, and 0.0072mol of 3, 4-dihydro-2H-pyran, 0.008mol of p-toluenesulfonic acid and THF solvent are added for reaction for 8H. After the reaction was complete, the reaction was carried out in 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a volume ratio of 1:3 for several times, and vacuum-drying the filter cake at 50 ℃ for 72h to obtain a powder of the alkali-soluble resin P7.

Preparation example 8: synthesis of alkali-soluble resin P8

ODA (0.018mol), 6FAP (0.018mol) and SiDA (0.002mol) were dissolved in NMP (100g) under a stream of dry nitrogen. ODPA (0.020mol), BTDA (0.020mol) and 40g of NMP were then added thereto, and the mixture was reacted at 25 ℃ for 2 hours. Then 3-aminophenol (0.0024mol) is added to react for 48h at 25 ℃, then the temperature is reduced to 0 ℃, 0.0042mol of propylene oxide and 0.004mol of A3 are added to react for 4h at 0 ℃. Finally, the temperature is raised to the room temperature, and 0.0108mol of 3, 4-dihydro-2H-pyran, 0.012mol of p-toluenesulfonic acid and THF solvent are added for reaction for 8H. After the reaction was complete, the reaction was carried out in 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a volume ratio of 1:3 for several times, and vacuum-drying the filter cake at 50 ℃ for 72h to obtain a powder of the alkali-soluble resin P8.

Preparation example 9: synthesis of alkali-soluble resin P9

6FODA (0.018mol), 6FAP (0.018mol) and SiDA (0.002mol) were dissolved in NMP (100g) under a stream of dry nitrogen. Subsequently, 6FDA (0.020mol), CBDA (0.020mol) and 40g of NMP were added thereto, and reacted at 25 ℃ for 2 hours. Then 3-aminophenol (0.0024mol) is added to react for 48h at 25 ℃, then the temperature is reduced to 0 ℃, 0.0042mol of propylene oxide and 0.004mol of A5 are added to react for 4h at 0 ℃. Finally, the temperature is raised to room temperature, and 0.0144mol of 3, 4-dihydro-2H-pyran, 0.015mol of p-toluenesulfonic acid and a solvent THF are added for reaction for 8H. After the reaction was complete, the reaction was carried out in 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a volume ratio of 1:3 for several times, and vacuum-drying the filter cake at 50 ℃ for 72h to obtain a powder of the alkali-soluble resin P9.

Examples of obtaining a polyamic acid containing a chemically amplified group and a polyamic acid containing a crosslinking-degrading group, respectively, and mixing the two polyamic acids:

preparation example 10: synthesis of alkali-soluble resin P10

Bis (4-aminophenyl) hexafluoropropane (0.018mol), 6FAP (0.018mol) and SiDA (0.002mol) were dissolved in NMP (100g) under a dry nitrogen stream. ODPA (0.020mol), BTDA (0.020mol) and 40g of NMP were then added thereto, and the mixture was reacted at 25 ℃ for 2 hours. Then adding 3-aminophenol (0.0024mol), reacting for 48h at 25 ℃, then cooling to 0 ℃, adding 0.0042mol of propylene oxide and 0.004mol of A3, and reacting for 4h at 0 ℃ to obtain the resin P10-1.

Bis (4-aminophenyl) hexafluoropropane (0.018mol), 6FAP (0.018mol) and SiDA (0.002mol) were dissolved in NMP (100g) under a dry nitrogen stream. ODPA (0.020mol), BTDA (0.020mol) and 40g of NMP were then added thereto, and the mixture was reacted at 25 ℃ for 2 hours. Then 3-aminophenol (0.0024mol) is added to react for 48h at 25 ℃, then 0.020mol of N, N-dimethylformamide di-tert-butyl acetal is added, and then the temperature is raised to 80 ℃ to react for 4 h. And after the reaction is finished, cooling to room temperature to obtain the resin P10-2.

Resin P10-1 and resin P10-2 were mixed at room temperature in an equimolar ratio, in 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a volume ratio of 1:3 for several times, and vacuum-drying the filter cake at 50 ℃ for 72h to obtain a powder of the alkali-soluble resin P10.

Preparation example 11: synthesis of alkali-soluble resin P11

ODA (0.018mol), 6FAP (0.018mol) and SiDA (0.002mol) were dissolved in NMP (100g) under a stream of dry nitrogen. Then, 6FDA (0.020mol), ODPA (0.020mol) and 40g of NMP were added thereto, and reacted at 25 ℃ for 2 hours. Then adding 3-aminophenol (0.0024mol), reacting for 48h at 25 ℃, then cooling to 0 ℃, adding 0.0042mol of propylene oxide and 0.004mol of A3, and reacting for 4h at 0 ℃ to obtain the resin P11-1.

ODA (0.018mol), 6FAP (0.018mol), and SiDA (0.002mol) were dissolved in NMP (100g) under a dry nitrogen stream. Then, 6FDA (0.020mol), ODPA (0.020mol) and 40g of NMP were added thereto and reacted at 25 ℃ for 2 hours. Then 3-aminophenol (0.0024mol) is added to react for 48h at 25 ℃, then 0.025mol of N, N-dimethylformamide di-tert-butyl acetal is added, and then the temperature is raised to 80 ℃ to react for 4 h. After the reaction is finished, the temperature is reduced to room temperature, and the resin P11-2 is obtained.

Resin P11-1 and resin P11-2 were mixed at room temperature in an equimolar ratio, in 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a volume ratio of 1:3 for several times, and vacuum-drying the filter cake at 50 ℃ for 72h to obtain a powder of the alkali-soluble resin P11.

Preparation example 12: synthesis of alkali-soluble resin P12

6FODA (0.018mol), 6FAP (0.018mol) and SiDA (0.002mol) were dissolved in NMP (100g) under a stream of dry nitrogen. BTDA (0.020mol), CBDA (0.020mol) and 40g of NMP were then added thereto, and reacted at 25 ℃ for 2 hours. Then adding 3-aminophenol (0.0024mol), reacting for 48h at 25 ℃, then cooling to 0 ℃, adding 0.0042mol of propylene oxide and 0.004mol of A3, and reacting for 4h at 0 ℃ to obtain the resin P12-1.

6FODA (0.018mol), 6FAP (0.018mol) and SiDA (0.002mol) were dissolved in NMP (100g) under a stream of dry nitrogen. BTDA (0.020mol), CBDA (0.020mol) and 40g of NMP were then added thereto, and reacted at 25 ℃ for 2 hours. Then 3-aminophenol (0.0024mol) is added to react for 48h at 25 ℃, then 0.030mol of N, N-dimethylformamide di-tert-butyl acetal is added, and then the temperature is raised to 80 ℃ to react for 4 h. After the reaction is finished, the temperature is reduced to room temperature, and the resin P12-2 is obtained.

Resin P12-1 and resin P12-2 were mixed at room temperature in an equimolar ratio, in 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a volume ratio of 1:3 for several times, and vacuum-drying the filter cake at 50 ℃ for 72h to obtain a powder of the alkali-soluble resin P12.

Comparative preparation example 1: synthesis of alkali-soluble resin P1-1

ODA (0.018mol), 6FAP (0.018mol) and SiDA (0.002mol) were dissolved in NMP (100g) under a stream of dry nitrogen. ODPA (0.020mol), BTDA (0.020mol) and 40g of NMP were then added thereto, and the mixture was reacted at 25 ℃ for 2 hours. Then 3-aminophenol (0.0024mol) is added to react for 48h at 25 ℃, then the temperature is reduced to 0 ℃, 0.0042mol of propylene oxide and 0.004mol of A3 are added to react for 4h at 0 ℃. Finally, the temperature is raised to room temperature, and the reaction is carried out in a 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a volume ratio of 1:3 for several times, and vacuum-drying the filter cake at 50 ℃ for 72h to obtain powder of the alkali-soluble resin P1-1.

Comparative preparation example 2: synthesis of alkali-soluble resin P1-2

ODA (0.018mol), 6FAP (0.018mol) and SiDA (0.002mol) were dissolved in NMP (100g) under a stream of dry nitrogen. ODPA (0.020mol), BTDA (0.020mol) and 40g of NMP were then added thereto, and the mixture was reacted at 25 ℃ for 2 hours. Then 3-aminophenol (0.0024mol) is added to react for 48h at 25 ℃, then the temperature is reduced to 0 ℃, 0.0042mol of propylene oxide and 0.004mol of A3 are added to react for 4h at 0 ℃. Finally, the temperature is raised to the room temperature, and 0.02mol of 3, 4-dihydro-2H-pyran, 0.022mol of p-toluenesulfonic acid and THF solvent are added for reaction for 8H. After the reaction was complete, the reaction was carried out in 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a volume ratio of 1:3 for several times, and vacuum-drying the filter cake at 50 ℃ for 72h to obtain powder of the alkali-soluble resin P1-2.

Comparative preparation example 3: synthesis of alkali-soluble resin P1-3

ODA (0.018mol), 6FAP (0.018mol) and SiDA (0.002mol) were dissolved in NMP (100g) under a stream of dry nitrogen. ODPA (0.020mol), BTDA (0.020mol) and 40g of NMP were then added thereto, and the mixture was reacted at 25 ℃ for 2 hours. Then 3-aminophenol (0.0024mol) was added and reacted at 25 ℃ for 48 hours. Finally, the temperature is raised to room temperature, and the reaction solution is stirred in a 2L ethanol: water in a 1:3 (volume ratio) solvent to give a white precipitate, which is filtered and the filter cake is washed with ethanol: washing with water at a volume ratio of 1:3 for several times, and vacuum-drying the filter cake at 50 ℃ for 72h to obtain powder of the alkali-soluble resin P1-3.

< preparation of Positive photosensitive resin composition >

Examples 1 to 12 and comparative examples 1 to 3

Examples 1 to 12 and comparative examples 1 to 3 provide a positive photosensitive resin composition prepared by the method comprising: 10g of the alkali-soluble resins prepared in preparation examples 1 to 12 and comparative preparation examples 1 to 3 were taken in this order, and a photoacid generator was added thereto: 1.2g PAC-1, addition of crosslinker: 1.5g of MX-270 (manufactured by Kyowa chemical Co., Ltd.) and 2.5g of EXA-4880 (Dainippon ink chemical Co., Ltd.) were added with a solvent: 10g of gamma-butyrolactone was added to prepare a varnish (i.e., the positive photosensitive resin composition of the present invention).

The positive photosensitive resin compositions prepared in inventive examples 1 to 12 and comparative examples 1 to 3 were identical except that the alkali-soluble resins used were the alkali-soluble resins prepared in preparation examples 1 to 12 and comparative preparation examples 1 to 3 in this order.

The varnish was applied to a silicon substrate using a spin coater, baked at 80 ℃ for 3min to form a coating film, and the coating film was exposed using a photolithography small-sized developing apparatus (AC3000, manufactured by greenling industries, ltd.). After exposure, postbaking was carried out at 110 ℃ for 3 min. Then, the resultant was developed with a 2.38 mass% aqueous tetramethylammonium hydroxide solution for 55 seconds and rinsed with water for 30 seconds. After the development and rinsing, the coating was thermally cured at 250 ℃ for 60 minutes using a high-temperature inert gas oven (INH-9 CD-S; manufactured by Koyo Thermo Systems Co., Ltd.) to prepare a cured film having a film thickness of about 1.5. mu.m.

The positive photosensitive resin compositions prepared in examples 1 to 12 of the present invention and comparative examples 1 to 3 were evaluated, respectively, to obtain the following table 1:

TABLE 1 evaluation of Properties of Positive photosensitive resin compositions prepared in examples 1 to 12 and comparative examples 1 to 3

< method for evaluating Positive photosensitive resin composition >

Evaluation of imaging ability: after the obtained envelope is subjected to the exposure, development and cleaning, the state of an etched line or groove is detected by using SEM (scanning Electron microscope), the line or groove with the width less than 5 mu m can still be clearly etched without bending and defect; the lines or grooves with the width of 5-20 mu m can be clearly etched without bending and defect; only the lines or grooves with the width of more than 20 mu m can be clearly etched, no bending exists, and no defect exists.

Sensitivity evaluation: the varnish was coated on a 6-inch silicon wafer by a spin coating method using a coating and developing apparatus ACT-8 (manufactured by Tokyo Electron Limited), and prebaked at 120 ℃ for 3 minutes. The exposure was performed using an i-line stepper NSR-2005i9C (manufactured by Nikon). After exposure, development was repeated 2 times by spin immersion (discharge time of developer solution was 10 seconds, spin immersion time was 40 seconds) using a developing apparatus of ACT-8 using a 2.38 wt% tetramethylammonium aqueous solution (hereinafter referred to as TMAH, manufactured by the multi-molar chemical industry), followed by rinsing with pure water and spin-drying, and the lowest exposure amount at which the exposed portion was completely dissolved was regarded as the sensitivity.

Evaluation of contrast γ: a contrast curve, which is a curve of the thickness of the resist (photosensitive resin composition) remaining after development as a function of exposure dose, was obtained in the same manner as in the sensitivity evaluation, and for the positive type resist, after reaching a critical value as the exposure dose increased, the thickness of the resist after development began to decrease until the exposure dose D reached₂When this happens, the photoresist disappears completely. The contrast γ was defined according to the following formula, and the exposure dose was measured in the same manner as the sensitivity evaluation method.

γ＝{lg(D₂/D₁)}^-1

Wherein D is₂Is the minimum exposure dose, mJ/cm, for complete photoresist disappearance²；D₁Is the maximum exposure dose, mJ/c, that keeps the photoresist thickness constantm²。

Claims

1. An alkali-soluble resin, characterized in that the alkali-soluble resin comprises a structure (a1) and a structure (a 2); the structure (a1) comprises structural formula (a11) and/or structural formula (a12), and the structure (a2) comprises any one or more of structural formula (a21), (a22) and (a 23);

r in the structural formula (a21)₀A hydrocarbon group having 1 to 4 carbon atoms, and a bond site in the structural formulae (a21), (a22), and (a 23);

the alkali soluble resin preferably comprises structure (a11) and structure (a 2).

2. The alkali-soluble resin according to claim 1, wherein the proportion of structural formula (a11) and/or structural formula (a12) in the alkali-soluble resin is 0.5 mol% to 20 mol%, preferably 0.5 mol% to 15 mol%, more preferably 0.5 mol% to 5 mol%;

the proportion of structural formula (a21) in the alkali-soluble resin is from 50 mol% to 80 mol%, preferably from 60 mol% to 70 mol%, and the proportion of structural formulae (a22), (a23) in the alkali-soluble resin is from 20 mol% to 40 mol%, preferably from 30 mol% to 40 mol%.

3. The alkali-soluble resin according to claim 1, wherein the alkali-soluble resin structure comprises structural formula (a3) and/or structural formula (a 4):

in the structural formulas (a3) and (a4), X, Y, Z, W represents a reaction residue of dianhydride, P, Q, R, S represents a reaction residue of diamine, wherein any one or more of P, Q, R, S and K comprises a structural formula (a11) and/or any one or more of structural formulas (a12), P, Q, R, S, X, Y, Z and W takes any one of structural formulas (a21), (a22) and (a23) as a substituent group, and L is₁、L₂Each represents a repeating unit, R₁、R₂H or an organic group containing 1 to 8 carbon atoms, a, b, c, d, e, f, g and H are integers of 0 to 4, a + b + c + d > 0, e + f + g + H > 0, and m, n, k and l are integers of 1 to 1000.

4. The alkali-soluble resin according to claim 1, wherein a component represented by the following general formula (K1) or (K2) is introduced into the polyimide precursor solution, and after the reaction, a compound having the structural formula (a21), (a22), (a23) is introduced;

in the general formula (K1) or (K2), A is an organic group having at least 6 carbons, R₃Is any organic radical, R₄Is a chlorine atom or optionally contains NH₂I1 and i2 represent polymerization degrees, i1 is not less than 1, and i2 is not less than 1.

5. The alkali-soluble resin according to claim 4, wherein the diamine for forming the polyimide precursor comprises an aliphatic diamine or an aromatic diamine, preferably a diamine containing a hydroxyl group; the dianhydride for forming the polyimide precursor includes an aromatic dianhydride, preferably a dianhydride other than a biphenyl structure.

6. The alkali-soluble resin according to claim 4, wherein R is₄Is a chlorine atom, preferably i1 is 1-4, i2 is 1-4; r₄Is optionally NH₂The organic group of (2) is added with the component shown in the general formula (K1) or (K2) after the diamine monomer and the dianhydride monomer are polymerized.

7. The alkali-soluble resin according to claim 4, wherein in the general formula (K1) or (K2), the functional group-N-O-CO-or-N-O-SO₂The number of-is 2, the molar mass of the formula (K1) or (K2) is less than or equal to 3000, preferably less than or equal to 2000; functional groups-N-O-CO-or-N-O-SO₂The number of-is not less than 3, the molar mass of the compounds of the formula (K1) or (K2) is not more than 50000, preferably not more than 20000.

8. A positive photosensitive resin composition comprising the alkali-soluble resin according to any one of claims 1 to 7, comprising:

(a) 100 parts by weight of an alkali-soluble resin;

(b) 10-40 parts of a photoacid generator;

(c) 10-60 parts of thermal cross-linking agent;

(d) an organic solvent.

9. A cured film obtained by coating, prebaking, exposing, postbaking, developing and curing the positive photosensitive resin composition according to claim 8.

10. A display device characterized by comprising the cured film according to claim 9.