Photosensitive resin composition and curable film

Abstract

A photosensitive resin composition includes a copolymer. The copolymer has a plurality of repeating units represented by formula (I) and a plurality of repeating units represented by formula (II), of which each symbol is defined in the specification. Therefore, the photosensitive resin composition has specific structure, which enhances the thermal properties, mechanical properties and chemical resistance of the cured product thereof.

Description

[Technical Field]

[0001] This disclosure relates to a resin composition and a curing film, and more particularly to a photosensitive resin composition and a curing film that can obtain good material properties at low curing temperatures. [Previous Technology]

[0002] Polyimide is a polymer material with a polyimide structure. It has good thermal stability, mechanical properties, electrical properties, low moisture absorption and chemical stability. Therefore, polyimide is one of the important high-performance polymer materials in the current semiconductor manufacturing process.

[0003] Conventional polyimide precursors require high-temperature baking to obtain the polyimide polymer, with baking temperatures reaching 230°C to 350°C, to ensure that the polyimide has a high glass transition temperature and good mechanical properties and chemical resistance. However, high-temperature baking can easily lead to residual stress on the substrate carrying the polyimide, causing the substrate to warp, resulting in excessive energy consumption and increased manufacturing costs. [Summary of the Invention]

[0004] The purpose of this disclosure is to provide a photosensitive resin composition and a curing film, wherein the curing temperature is reduced and good material properties are maintained by adjusting the chemical structure of the photosensitive resin composition.

[0005] One embodiment of this disclosure provides a photosensitive resin composition comprising a polymer having a plurality of repeating units as shown in Formula (I) and a plurality of repeating units as shown in Formula (II): Formula (I), Equation (II); Wherein, A is a tetravalent organogroup with 6 to 40 carbon atoms, B1 and B2 are each independently a divalent organogroup with 6 to 40 carbon atoms, C is a trivalent to hexavalent organogroup with 6 to 40 carbon atoms, R1 is a photosensitive crosslinking group, and R2 has a structure as shown in formula (II-a) or formula (II-b): Formula (II-a), Equation (II-b); Where R0 is a hydrogen atom or a methyl group, and X is an enylmethyl group, an oxygen atom, or a sulfur atom, n is an integer greater than or equal to 1, m is an integer greater than or equal to 1, and y is an integer from 1 to 3. When X is an enylmethyl group, the following condition is satisfied: 0.1 ≤ the molar ratio of the repeating unit as shown in formula (II) to all repeating units of the polymer ≤ 0.4.

[0006] Another embodiment of this disclosure provides a photosensitive resin composition comprising a thermal alkali generating agent and a polymer. The polymer has a plurality of repeating units as shown in formula (I) and a plurality of repeating units as shown in formula (II): Formula (I), Equation (II); Wherein, A is a tetravalent organogroup with 6 to 40 carbon atoms, B1 and B2 are each independently a divalent organogroup with 6 to 40 carbon atoms, C is a trivalent to hexavalent organogroup with 6 to 40 carbon atoms, R1 is a photosensitive crosslinking group, and R2 has a structure as shown in formula (II-a) or formula (II-b): Formula (II-a), Equation (II-b); Where R0 is a hydrogen atom or a methyl group, and X is a protylmethyl group, an oxygen atom, or a sulfur atom, n is an integer greater than or equal to 1, m is an integer greater than or equal to 1, and y is an integer from 1 to 3.

[0007] According to the aforementioned photosensitive resin composition, A may be a tetravalent organic group containing 1 to 4 benzene rings, B1 and B2 may each be a divalent organic group containing 1 to 4 benzene rings, and C may be a trivalent to hexavalent organic group containing 1 to 4 benzene rings.

[0008] According to the aforementioned photosensitive resin composition, at least one of the benzene rings of A, B1, B2 and C may have at least one linking group, and the linking group may be a divalent organic group having 1 to 6 carbon atoms.

[0009] According to the aforementioned photosensitive resin composition, the linker may include at least one selected from the group consisting of oxygen atom, nitrogen atom, sulfur atom, alkenyl group, alkynyl group, ester group, ether group and ketone group.

[0010] According to the aforementioned photosensitive resin composition, R1 may have a structure as shown in formula (III): Equation (III); R3 can be an alkyl group having 1 to 8 carbon atoms, and R4 can be a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0011] According to the aforementioned photosensitive resin composition, n may be an integer from 1 to 150, and m may be an integer from 1 to 150.

[0012] The aforementioned photosensitive resin composition may further include a thermal crosslinking agent.

[0013] According to the aforementioned photosensitive resin composition, the thermal crosslinking agent may have a thermally reactive functional group, and the thermally reactive functional group may be selected from at least one of the group consisting of hydroxymethyl, alkoxymethyl, ethylene oxide, isocyanate, bismaleimino, alkenyl and alkynyl.

[0014] The aforementioned photosensitive resin composition may further include at least one of a photoinitiator and a multifunctional acrylic photocrosslinker.

[0015] According to the aforementioned photosensitive resin composition, the thermal alkali generating agent may have at least one of a structure shown in formula (IV) and a structure shown in formula (V): Formula (IV), Formula (V); Among them, R5, R6, R7, R8, R9 and R10 can each be a hydrogen atom, an aromatic cycloalgyl group or an alkyl group, and R11 can be an alkylene group.

[0016] According to the aforementioned photosensitive resin composition, at least one of R5, R6, R7, R8, R9, R10 and R11 may be replaced by at least one selected from the group consisting of oxygen atom, nitrogen atom, sulfur atom, alkenyl group, alkynyl group, ether group and ketone group.

[0017] According to the aforementioned photosensitive resin composition, the thermal alkali generating agent may have at least one of a structure shown in formula (IV) and a structure shown in formula (V): Formula (IV), Formula (V); Among them, at least one of R5 and R6, R7 and R8, R9 and R10, and R9 and R11 can be bonded to form a ring structure.

[0018] According to the aforementioned photosensitive resin composition, the polymer may be a copolymer.

[0019] Another embodiment of this disclosure provides a hardened film, which is cured from the aforementioned photosensitive resin composition. The repeating unit shown in formula (I) in the photosensitive resin composition undergoes a cyclization reaction to form a plurality of repeating units as shown in formula (I-1): Formula (I-1).

[0020] Based on the aforementioned hardened membrane, the cyclization rate of the hardened membrane can be above 80%.

[0021] Accordingly, the photosensitive resin composition disclosed herein has a specific structure that facilitates polymer rearrangement and crosslinking reactions, and increases the crosslinking density of the polymer's polymer chains. Therefore, it still maintains a high glass transfer temperature at low-temperature baking temperatures (≤ 200°C), improving the thermal and mechanical properties of the cured product. On the other hand, by adding a thermal alkali generating agent, it maintains a high cyclization rate and good chemical resistance even at low-temperature processes (≤ 200°C). Furthermore, the photosensitive crosslinking groups in the polymer provide photosensitivity, so patterning can be performed through exposure and development. Therefore, the photosensitive resin composition can simultaneously possess the characteristics of both insulating and photoresist materials, helping to reduce process steps, lower costs, and improve yield.

Implementation Method

[0022] The various embodiments of this disclosure will be discussed in more detail below. However, this embodiment can be an application of various disclosed concepts and can be implemented in various different specific scopes. The specific embodiments are for illustrative purposes only and are not limited to the scope of the disclosure.

[0023] In this disclosure, the compound structure is sometimes represented by a skeleton formula, which can omit carbon atoms, hydrogen atoms, and carbon-hydrogen bonds. If the functional group is clearly drawn in the structural formula, the drawing shall prevail.

[0024] One embodiment of this disclosure provides a photosensitive resin composition comprising a polymer having a plurality of repeating units as shown in Formula (I) and a plurality of repeating units as shown in Formula (II): Formula (I), Equation (II); Wherein, A is a tetravalent organogroup with 6 to 40 carbon atoms, B1 and B2 are each independently a divalent organogroup with 6 to 40 carbon atoms, C is a trivalent to hexavalent organogroup with 6 to 40 carbon atoms, R1 is a photosensitive crosslinking group, and R2 has a structure as shown in formula (II-a) or formula (II-b): Formula (II-a), Equation (II-b); Where R0 is a hydrogen atom or a methyl group, and X is an enylmethyl group, an oxygen atom, or a sulfur atom, n is an integer greater than or equal to 1, m is an integer greater than or equal to 1, and y is an integer from 1 to 3. When X is an enylmethyl group, the following condition is satisfied: 0.1 ≤ the molar ratio of the repeating unit as shown in formula (II) to all repeating units of the polymer ≤ 0.4. Wherein, when the condition 0.1 ≤ the molar ratio of the repeating unit as shown in formula (II) to all repeating units of the polymer ≤ 0.4 is satisfied, the effect on improving the thermal properties of the photosensitive resin composition, such as the storage modulus (E') or glass transition temperature (Tg), is more significant, and after exposure, crosslinking is easier to perform to produce development contrast.

[0025] In detail, the plurality of repeating units shown in formula (I) are formed by the reaction of a dianhydride compound and a diamine compound, and the plurality of repeating units shown in formula (II) are formed by the reaction of a dianhydride compound and a diamine compound. The dianhydride compound may contain a plurality of dianhydride monomers, and the dianhydride monomers may contain at least one of aromatic dianhydrides and alicyclic dianhydrides. The aromatic dianhydrides may be selected from at least one of the group consisting of formulas (a), (b), (c), (d), (e), and (f): Equation (a) Formula (b) Equation (c) Formula (d) Equation (e) Equation (f); Alicyclic dianhydrides can be selected from at least one of the groups consisting of free formula (g), formula (h), and formula (i): Formula (g) Formula (h) Formula (i); Among them, the use of aromatic dianhydrides is beneficial to improving the mechanical properties of the subsequently produced hardened film, while the use of alicyclic dianhydrides is beneficial to improving the electrical properties of the hardened film.

[0026] The diamine compound may comprise a plurality of diamine monomers, wherein the diamine monomers may comprise at least one of aromatic diamines and alicyclic diamines, and the aromatic diamines may be selected from at least one of the group consisting of free formula (j), formula (k), formula (l), formula (m), formula (n), formula (o), formula (p), formula (q), formula (r), formula (s), formula (t), formula (u), formula (v) and formula (w): Equation (j) Equation (k) Formula (l) Formula (m) Equation (n) Formula (o) Formula (p) Formula (q) Formula (r), Formula (s), Formula (t), Formula (u), Formula (v) Formula (w); Alicyclic diamines can be, for example, represented by the structure shown in formula (x): Equation (x).

[0027] Another embodiment of this disclosure provides a photosensitive resin composition comprising a thermal alkali generating agent and a polymer. The polymer has a plurality of repeating units as shown in formula (I) and a plurality of repeating units as shown in formula (II): Formula (I), Equation (II); Wherein, A is a tetravalent organogroup with 6 to 40 carbon atoms, B1 and B2 are each independently a divalent organogroup with 6 to 40 carbon atoms, C is a trivalent to hexavalent organogroup with 6 to 40 carbon atoms, R1 is a photosensitive crosslinking group, and R2 has a structure as shown in formula (II-a) or formula (II-b): Formula (II-a), Equation (II-b); Where R0 is a hydrogen atom or a methyl group, and X is a protylmethyl group, an oxygen atom, or a sulfur atom, n is an integer greater than or equal to 1, m is an integer greater than or equal to 1, and y is an integer from 1 to 3.

[0028] In another embodiment of this disclosure, the repeating unit shown in formula (I) in the polymer can independently form a first polymer, and the repeating unit shown in formula (II) can independently form a second polymer. That is, the polymer can be a polymer blend containing the first polymer and the second polymer. Alternatively, the repeating units shown in formula (I) and the repeating units shown in formula (II) in the polymer can form a copolymer, and the copolymer can be combined in the form of a random copolymer or a block copolymer.

[0029] Accordingly, since the polymer in the photosensitive resin composition disclosed herein has a structure as shown in formula (II-a) or formula (II-b), it facilitates the rearrangement and crosslinking reaction of the polymer and increases the crosslinking density of the polymer's polymer chains. Therefore, a higher glass transition temperature can be obtained at a low curing temperature, and the cured product also has good thermal properties (such as storage modulus or weight loss) and mechanical properties. On the other hand, by adding a hot alkali generating agent, a high cyclization rate and good chemical resistance are maintained even at low temperature processes (≤ 200°C). In addition, the photosensitive crosslinking groups in the polymer provide photosensitivity, so patterning can be performed through exposure and development. Therefore, the photosensitive resin composition can simultaneously possess the characteristics of an insulating material and a photoresist material, which helps to reduce process steps, lower costs, and improve yield.

[0030] Furthermore, A may be a tetravalent organogroup containing 1 to 4 benzene rings, B1 and B2 may each be independently a divalent organogroup containing 1 to 4 benzene rings, and C may be a trivalent to hexavalent organogroup containing 1 to 4 benzene rings. At least one linker may be present between the benzene rings of at least one of A, B1, B2, and C, and the linker may be a divalent organogroup having 1 to 6 carbon atoms. The linker may include at least one group selected from the group consisting of oxygen, nitrogen, sulfur, alkenyl, alkynyl, ester, ether, and ketone groups.

[0031] Furthermore, R1 may have a structure as shown in equation (III): Equation (III); R3 can be an alkyl group having 1 to 8 carbon atoms, and R4 can be a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0032] Furthermore, n can be an integer from 1 to 150, and m can be an integer from 1 to 150.

[0033] Furthermore, the weight average molecular weight (Mw) of the polymer can be 10,000 to 50,000, preferably 20,000 to 40,000. Controlling the weight average molecular weight of the polymer is beneficial to the formation of patterns.

[0034] Furthermore, the photosensitive resin composition may further include a thermal crosslinking agent, which helps to promote the crosslinking reaction during the curing of the photosensitive resin composition and improves the properties of the cured product. The thermal crosslinking agent may have a thermally reactive functional group, and the thermally reactive functional group may be selected from at least one of the group consisting of hydroxymethyl (-CH2OH), alkoxymethyl (-CH2OR), ethylene oxide, isocyanate, bismaleimide, alkenyl, and alkynyl, wherein R may be an alkyl group, preferably an alkyl group having 1 to 3 carbon atoms, but not limited thereto. The proportion of the thermal crosslinking agent in the photosensitive resin composition may be 0.1% to 20%, preferably 0.1% to 10%, and more preferably 3% to 5%. In addition, the crosslinking temperature of the thermal crosslinking agent may be 120°C to 170°C.

[0035] The photosensitive resin composition may further include at least one of a photoinitiator and a multifunctional acrylic photocrosslinker, which helps to promote the photocuring reaction of the photosensitive resin composition. The photoinitiator may be selected from at least one of the group consisting of phosphine oxide compounds, transition metal compounds, oxime compounds, benzophenone derivatives, α-hydroxy ketone compounds, and α-aminoalkyl phenyl ketone compounds. The proportion of the photoinitiator in the photosensitive resin composition may be from 0.1% to 5%.

[0036] The hot alkali generating agent can generate an alkaline substance during heating in a low-temperature process to promote the cyclization reaction of the photosensitive resin composition. Another embodiment of this disclosure provides a hot alkali generating agent that may have at least one of a structure shown in formula (IV) and a structure shown in formula (V): Formula (IV), Formula (V);

[0037] Wherein, R5, R6, R7, R8, R9, and R10 may each be independently a hydrogen atom, an aromatic cycloyl group, or an alkyl group, and R11 may be an alkylene group. Furthermore, at least one of R5, R6, R7, R8, R9, R10, and R11 may be substituted by at least one of the group consisting of oxygen, nitrogen, sulfur, alkenyl, alkynyl, etheryl, and ketone groups. Furthermore, at least one of R5 and R6, R7 and R8, R9 and R10, and R9 and R11 may be bonded to form a cyclic structure.

[0038] Furthermore, the proportion of the thermal alkali generating agent in the photosensitive resin composition can be from 0.1% to 5%, preferably from 0.1% to 1%. The decomposition temperature of the alkaline substance generated by the thermal alkali generating agent can be from 100°C to 170°C, and the acid dissociation constant (pKa) of the conjugate acid of the alkaline substance can be greater than 5.

[0039] Furthermore, the alkaline substance produced by the hot alkali generating agent can be an organic base, and can be a primary amine, secondary amine, tertiary amine, amidine, or guanidine. Furthermore, the hot alkali generating agent can be an ionic hot alkali generating agent, which includes a cation and an anion. The cation can be selected from the group consisting of primary amines, secondary amines, tertiary amines, amidine, and guanidine. The anion can include organic acid anions or inorganic acid anions, or the anion can be selected from the group consisting of carboxylate anions, sulfate anions, phosphate anions, and phenols.

[0040] In another embodiment of this disclosure, the photosensitive resin composition may further include a photopolymerizable monomer to enhance the photosensitivity of the photosensitive resin composition. The photopolymerizable monomer may have unsaturated double bonds, and may have two or more unsaturated double bonds. Furthermore, the photopolymerizable monomer may include an acrylic compound, and may be selected from the group consisting of ethylene glycol dimethacrylate, pentaerythritol diacrylate, and dipentaerythritol hexaacrylate. Furthermore, the proportion of the photopolymerizable monomer in the photosensitive resin composition may be from 1% to 30%.

[0041] In another embodiment of the present disclosure, the photosensitive resin composition may further include a solvent, which may include, but is not limited to, γ-butyrolactone, N-methylpyrrolidone, dimethyl sulfoxide, N-ethylpyrrolidone, dimethylformamide or dimethylacetamide, and the solvent accounts for a proportion of 30% to 80% of the photosensitive resin composition.

[0042] In another embodiment of the present disclosure, the photosensitive resin composition may further include other additives, such as at least one of leveling agents, heterojunction promoters, sensitizers and antioxidants, to improve the processability, stability and finished product characteristics of the photosensitive resin composition.

[0043] Another embodiment of this disclosure provides a hardened film, which is cured from the aforementioned photosensitive resin composition. The repeating unit in the photosensitive resin composition, as shown in formula (I), undergoes a cyclization reaction to form a plurality of repeating units as shown in formula (I-1): Formula (I-1).

[0044] Furthermore, the cyclization rate of the hardened film can be 80% or more, so the aforementioned photosensitive resin composition can have excellent cyclization characteristics during curing.

[0045] The following specific embodiments further illustrate the present disclosure, so as to enable those skilled in the art to fully utilize and practice the present disclosure without excessive interpretation. These embodiments should not be regarded as a limitation on the scope of the present disclosure, but are used to illustrate how to implement the materials and methods of the present disclosure.

[0046] <Synthesis Example>

[0047] Synthesis Example 1: In a 1 L three-necked flask, ODPA (55 mmol; 17.1 g), PMDA (30 mmol; 6.5 g), HEMA (170 mmol; 22.1 g), pyridine (170 mmol; 13.5 g), and GBL (200 g) were added. The mixture was heated to 60°C and stirred for 2 hours, then cooled in an ice bath. Next, a diacid compound (15 mmol; 4.9 g) as shown in formula (II-b-1) was added. Then, through a feed tube, DCC solution (200 mmol; 41.2 g of DCC dissolved in 50 g of GBL), mMEA solution (30.3 mmol; 8.5 g of mMEA dissolved in 100 g of GBL), and m-tolidine solution (70.7 mmol; 15.0 g of m-tolidine dissolved in 100 g of GBL) were added dropwise. The reaction mixture was stirred in an ice bath for 18 hours, and the precipitate was removed by filtration. The resulting reaction solution was then added dropwise to 4 L of water. The solid was then filtered, separated, and vacuum dried to obtain the polymer of Synthetic Example 1. The calculated ratio of the repeating unit as shown in Formula (II) to all repeating units of the polymer in Synthetic Example 1 was 0.15.

[0048] The weight-average molecular weight of the polymer was determined by gel permeation chromatography (GPC) using standard polystyrene as a calibration conversion. The weight-average molecular weight of the polymer synthesized in Example 1 was 28,500.

[0049] Furthermore, the reactants of Synthesis Example 1 can undergo a chemical reaction as shown in Formula (A) to obtain the polymer of Synthesis Example 1: Formula (A).

[0050] In detail, the diacid compound represented by formula (II-b-1) is prepared by the following steps: 5-aminoisophthalic acid (450 mmol; 81.5 g), nadic anhydride (5-norbornene-2,3-dicarboxylic anhydride; 450 mmol; 73.8 g), and dimethylformamide (DMF; 450 mL) are added to a 1 L three-necked flask. The mixture is stirred at room temperature for 18 hours. Then, sodium acetate (135 mmol; 11.1 g) and acetic anhydride (1.5 mol; 153 g) are added. After stirring at 60°C for 2 hours, the mixture is cooled to room temperature and poured into 2 L of dilute hydrochloric acid (1 M). The resulting solid is then filtered and separated. After vacuum drying, the diacid compound represented by formula (II-b-1) is obtained.

[0051] It should be specifically noted that the A, X, B1, B2, and R1 groups in formula (A) may have different chemical structures depending on the reactants used. For example, the dianhydride compound used in synthesis example 1 contains ODPA and PMDA, therefore the A group in formula (A) can be any aromatic group in ODPA or PMDA. Furthermore, the diamine compound used in synthesis example 1 is mMEA and m-tolidine, therefore H2N-B1-N2H in formula (A) can be any mMEA or m-tolidine, and H2N-B2-N2H can also be any mMEA or m-tolidine. That is, in the polymer structure shown in formula (A), the A, B1, and B2 groups are not limited to a specific structure; they can be any combination of the dianhydride compound and the diamine compound used. Moreover, the reaction mechanisms of subsequent synthesis examples and comparative synthesis examples are the same as or similar to those of synthesis example 1, and will not be repeated here.

[0052] Synthesis Example 2: The synthesis steps of the polymer in Synthesis Example 2 are the same as those in Synthesis Example 1, except that the reactants used in Synthesis Example 2 are ODPA (40 mmol; 12.4 g), PMDA (30 mmol; 6.5 g), HEMA (140 mmol; 18.2 g), pyridine (140 mmol; 11.1 g), GBL (200 g), diacid compound as shown in formula (II-b-1) (30 mmol; 9.8 g), DCC solution (200 mmol; 41.2 g of DCC dissolved in 50 g of GBL), mMEA solution (10 mmol; 2.8 g of mMEA dissolved in 50 g of GBL) and m-tolidine solution (91 mmol; 19.3 g of m-tolidine dissolved in 150 g of GBL). The polymer of Synthetic Example 2 has a weight-average molecular weight of 21,100, wherein the calculated ratio of the repeating unit as shown in Formula (II) to all repeating units of the polymer in Synthetic Example 2 is 0.30.

[0053] Synthesis Example 3: The synthesis steps of the polymer in Synthesis Example 3 were the same as those in Synthesis Example 1, except that the reactants used in Synthesis Example 3 were ODPA (50 mmol; 15.5 g), PMDA (30 mmol; 6.5 g), HEMA (160 mmol; 20.8 g), pyridine (160 mmol; 12.7 g), GBL (200 g), DCC solution (200 mmol; 41.2 g of DCC dissolved in 50 g of GBL) and m-tolidine solution (101 mmol; 21.4 g of m-tolidine dissolved in 200 g of GBL). Furthermore, mMEA solution was not used in Synthesis Example 3, and the diacid compound shown in Formula (II-b-1) was replaced with the diacid compound shown in Formula (II-b-2) (20 mmol; 6.6 g). The polymer of Synthetic Example 3 has a weight-average molecular weight of 23,100, wherein the calculated ratio of the repeating unit as shown in Formula (II) to all repeating units of the polymer in Synthetic Example 3 is 0.20.

[0054] The preparation method of the diacid compound shown in formula (II-b-2) is similar to that of the diacid compound shown in formula (II-b-1) above, except that the nadic anhydride needs to be replaced with 3,6-oxo-1,2,3,6-tetrahydrophthalic anhydride.

[0055] Synthesis Example 4: The synthesis steps of the polymer in Synthesis Example 4 are the same as those in Synthesis Example 1, except that the reactants used in Synthesis Example 4 are ODPA (40 mmol; 12.4 g), PMDA (30 mmol; 6.5 g), HEMA (140 mmol; 18.2 g), pyridine (140 mmol; 11.1 g), GBL (200 g), DCC solution (200 mmol; 41.2 g of DCC dissolved in 50 g of GBL) and m-tolidine solution (81 mmol; 17.2 g of m-tolidine dissolved in 150 g of GBL). In Synthesis Example 4, the mMEA solution is replaced with the ODA solution (20 mmol; 4 g of ODA dissolved in 50 g of GBL), and the diacid compound shown in formula (II-b-1) is replaced with the diacid compound shown in formula (II-b-2) (30 mmol; 9.9 g). The polymer of Synthetic Example 4 has a weight-average molecular weight of 19,700, wherein the calculated ratio of the repeating unit as shown in Formula (II) to all repeating units of the polymer in Synthetic Example 4 is 0.30.

[0056] Synthesis Example 5: The synthesis steps of the polymer in Synthesis Example 5 are the same as those in Synthesis Example 1, except that the reactants used in Synthesis Example 5 are ODPA (40 mmol; 12.4 g), HEMA (140 mmol; 18.2 g), pyridine (140 mmol; 11.1 g), GBL (200 g), DCC solution (200 mmol; 41.2 g of DCC dissolved in 50 g of GBL) and m-tolidine solution (101 mmol; 21.4 g of m-tolidine dissolved in 200 g of GBL). Furthermore, mMEA solution was not used in Synthesis Example 5, and PMDA was replaced with BPDA (30 mmol; 8.8 g) and the diacid compound shown in formula (II-b-1) was replaced with the diacid compound shown in formula (II-b-2) (30 mmol; 9.9 g). The polymer of Synthetic Example 5 has a weight-average molecular weight of 24,500, wherein the calculated ratio of the repeating unit as shown in Formula (II) to all repeating units of the polymer in Synthetic Example 5 is 0.30.

[0057] Synthesis Example 6: The synthesis steps of the polymer in Synthesis Example 6 were the same as those in Synthesis Example 1, except that the reactants used in Synthesis Example 6 were ODPA (55 mmol; 17.1 g), PMDA (30 mmol; 6.5 g), HEMA (170 mmol; 22.1 g), pyridine (170 mmol; 13.5 g), GBL (200 g), DCC solution (200 mmol; 41.2 g of DCC dissolved in 50 g of GBL) and m-tolidine solution (101 mmol; 21.4 g of m-tolidine dissolved in 200 g of GBL), and mMEA solution was not used in Synthesis Example 6. The diacid compound shown in formula (II-b-1) was replaced with the diacid compound shown in formula (II-b-3) (15 mmol; 8.8 g). The polymer of Synthetic Example 6 has a weight-average molecular weight of 18,500, wherein the calculated ratio of the repeating unit as shown in Formula (II) to all repeating units of the polymer in Synthetic Example 6 is 0.15.

[0058] The preparation method of the diacid compound shown in formula (II-b-3) is similar to that of the diacid compound shown in formula (II-b-1) above, except that 5-aminoisophthalic acid needs to be replaced with bis(4-amino-3-carboxyphenyl)methane.

[0059] Synthesis Example 7: The synthesis steps of the polymer in Synthesis Example 7 were the same as those in Synthesis Example 1, except that the reactants used in Synthesis Example 7 were ODPA (40 mmol; 12.4 g), PMDA (30 mmol; 6.5 g), HEMA (140 mmol; 18.2 g), pyridine (140 mmol; 11.1 g), GBL (200 g), DCC solution (200 mmol; 41.2 g of DCC dissolved in 50 g of GBL) and m-tolidine solution (101 mmol; 21.4 g of m-tolidine dissolved in 200 g of GBL). Furthermore, mMEA solution was not used in Synthesis Example 7, and the diacid compound shown in Formula (II-b-1) was replaced with the diacid compound shown in Formula (II-a-1) (30 mmol; 8.3 g). The polymer of Synthetic Example 7 has a weight-average molecular weight of 31,300, wherein the calculated ratio of the repeating unit as shown in Formula (II) to all repeating units of the polymer in Synthetic Example 7 is 0.30.

[0060] The preparation method of the diacid compound shown in formula (II-a-1) is similar to that of the diacid compound shown in formula (II-b-1) above, except that nadic anhydride needs to be replaced with methylmaleic anhydride.

[0061] <Comparative Example of Synthesis>

[0062] Comparative Example 1: The synthesis steps of the polymer in Comparative Example 1 were the same as those in Comparative Example 1, except that the reactants used in Comparative Example 1 were ODPA (60 mmol; 18.6 g), PMDA (40 mmol; 8.7 g), HEMA (200 mmol; 26 g), pyridine (200 mmol; 15.8 g), GBL (200 g), DCC solution (200 mmol; 41.2 g of DCC dissolved in 50 g of GBL), mMEA solution (10 mmol; 2.8 g of mMEA dissolved in 50 g of GBL), and m-tolidine solution (91 mmol; 19.3 g of m-tolidine dissolved in 150 g of GBL), and no diacid compound was used in Comparative Example 1. The weight-average molecular weight of the polymer in Comparative Example 1 was 22,000.

[0063] Comparative Example 2: The synthesis steps of the polymer in Comparative Example 2 were the same as those in Comparative Example 1, except that the reactants used in Comparative Example 2 were ODPA (40 mmol; 12.4 g), PMDA (30 mmol; 6.5 g), HEMA (140 mmol; 18.2 g), pyridine (140 mmol; 11.1 g), GBL (200 g), DCC solution (200 mmol; 41.2 g of DCC dissolved in 50 g of GBL) and m-tolidine solution (101 mmol; 21.4 g of m-tolidine dissolved in 200 g of GBL). In Comparative Example 2, mMEA solution was not used, and the diacid compound shown in formula (II-b-1) was replaced with the diacid compound shown in formula (II-b-4) (30 mmol; 5.0 g). The polymer of Comparative Example 2 has a weight average molecular weight of 29,700. The calculated ratio of the repeating unit as shown in Formula (II) to all repeating units of the polymer in Comparative Example 2 is 0.3.

[0064] Comparative Example 3: The synthesis steps of the polymer in Comparative Example 3 were the same as those in Comparative Example 1. However, the reactants used in Comparative Example 3 were ODPA (95 mmol; 29.5 g), HEMA (190 mmol; 24.7 g), pyridine (190 mmol; 15.0 g), GBL (350 g), a diacid compound as shown in formula (II-b-1) (5 mmol; 1.6 g), and DCC solution (200 mmol; 41.2 g of DCC dissolved in 50 g of GBL). In Comparative Example 3, PMDA and m-tolidine solution were not used, and the mMEA solution was replaced with ODA solution (103 mmol; 20.6 g of ODA dissolved in 200 g of GBL). The polymer of Comparative Example 3 has a weight average molecular weight of 37,900. The calculated ratio of the repeating unit as shown in Formula (II) to all repeating units in the polymer of Comparative Example 3 is 0.05.

[0065] Comparative Example 4: The synthesis steps of the polymer in Comparative Example 4 were the same as those in Comparative Example 1, except that the reactants used in Comparative Example 4 were ODPA (40 mmol; 12.4 g), PMDA (60 mmol; 13.1 g), HEMA (200 mmol; 26.0 g), pyridine (200 mmol; 15.82 g), GBL (150 g), a diacid compound as shown in formula (II-b-1) (100 mmol; 32.9 g), DCC solution (400 mmol; 82.4 g of DCC dissolved in 50 g of GBL) and m-tolidine solution (202 mmol; 42.9 g of m-tolidine dissolved in 200 g of GBL), and mMEA solution was not used in Comparative Example 4. The polymer of Comparative Example 4 has a weight average molecular weight of 20,000. The calculated ratio of the repeating unit as shown in Formula (II) to all repeating units in the polymer of Comparative Example 4 is 0.5.

[0066] The reactants used in the above synthesis examples and comparative synthesis examples are listed in Table 1 below, and the diacid compounds and their chemical structures are listed in Table 2 below: Table 1 abbreviation Chemical structural formula and / or chemical name ODPA (Diphenyl ether-3,3',4,4'-tetracarboxylic acid dianhydride) PMDA (Pyromellitic anhydride) HEMA 2-Hydroxyethyl methacrylate pyridine Pyridine GBL γ-Butyrolactone DCC N,N'-dicyclohexylcarbodiimide mMEA (4,4'-Methylenebis(2-methyl-6-ethylaniline)) m-tolidine (2,2'-Dimethyl-4,4'-Diaminobiphenyl) ODA (4,4'-Diaminodiphenyl ether) BPDA (Biphenyl-3,3',4,4'-tetracarboxylic acid dianhydride) Table 2 Equation (II-b-1) Equation (II-b-2) Equation (II-b-3) Formula (II-a-1) Equation (II-b-4)

[0067] <Example>

[0068] The hardened films of Examples 1 to 10 were obtained by preparing a photosensitive resin composition using the polymers of Synthetic Examples 1 to 7 according to the component ratios in Tables 3-1 and 3-2 below, and then curing it: Table 3-1 Example polymer Hot alkali generating agent Photoinitiator thermal crosslinking agent Synthesis Examples Quality type Quality type Quality type Quality 1 1 32.7 DBU-MA 0.3 OXE-01 1.5 TAIC 2.25 2 2 32.7 DBU-MA 0.3 OXE-01 1.5 PC74 2.25 3 2 32.7 DBU-MA 0.3 OXE-01 1.5 TMOMBP 2.25 4 3 32.7 DBU-MA 0.3 OXE-01 1.5 PC74 2.25 5 4 32.7 5002 0.3 OXE-01 1.5 PC74 2.25 6 4 32.7 TMG-MA 0.3 OXE-01 1.5 PC74 2.25 7 4 32.7 DIPEA-MA 0.3 OXE-01 1.5 PC74 2.25 8 5 32.7 DBU-MA 0.5 OXE-01 1.5 PC74 2.25 9 6 32.7 DBU-MA 0.3 OXE-01 1.5 BMI 2.25 10 7 32.7 DBU-MA 0.3 OXE-01 1.5 BMI 2.25 Table 3-2 Example Photopolymerizable monomers solvent Other additives Curing conditions (°C / time) type Quality type Quality Quality 1 EM2308 5.9 GBL / NEP 55 2.35 200 / 1 hr 2 EM2308 5.9 GBL / NEP 55 2.35 200 / 1 hr 3 EM2308 5.9 GBL / NEP 55 2.35 200 / 1 hr 4 EM2308 5.9 GBL / NEP 55 2.35 190 / 2 hr 5 EM2308 5.9 GBL / NEP 55 2.35 190 / 2 hr 6 EM2308 5.9 GBL / NEP 55 2.35 190 / 2 hr 7 EM2308 5.9 GBL / NEP 55 2.35 190 / 2 hr 8 EM2308 5.9 GBL / NEP 55 2.15 190 / 2 hr 9 EM2308 5.9 GBL / NEP 55 2.35 170 / 3 hr 10 EM2308 5.9 GBL / NEP 55 2.35 170 / 3 hr

[0069] <Comparative example>

[0070] The hardened films of Comparative Examples 1 to 4 were obtained by preparing the polymers of Comparative Examples 1 to 4 into photosensitive resin compositions according to the component ratios in Tables 4-1 and 4-2 below, and then curing them: Table 4-1 Comparative example polymer Thermal alkali generator Photoinitiator Thermal crosslinking agent Synthetic comparative example mass Kind mass Kind mass Kind mass 1 1 32.7 DBU-MA 0.3 OXE-01 1.5 TAIC 2.25 2 2 32.7 DBU-MA 0.3 OXE-01 1.5 PC74 2.25 3 3 32.7 - - OXE-01 1.5 PC74 2.25 4 4 32.7 - - OXE-01 1.5 PC74 2.25 Table 4-2 Comparative example Photopolymerizable monomers solvent Other additives Curing conditions (°C / time) type Quality type Quality Quality 1 EM2308 5.9 GBL / NEP 55 2.35 200 / 1 hr 2 EM2308 5.9 GBL / NEP 55 2.35 190 / 2 hr 3 EM2308 5.9 GBL / NEP 55 2.35 190 / 2 hr 4 EM2308 5.9 GBL / NEP 55 2.35 190 / 2 hr

[0071] The components used in the above embodiments and comparative examples are listed in Table 5 below: Table 5 abbreviation Chemical structural formula and / or chemical name Hot alkali generating agent DBU-MA 5002 TMG-MA DIPEA-MA Photoinitiator OXE-01 Photoinitiator manufactured by BASF, product number OXE-01 thermal crosslinking agent TAIC PC74 TMOMBP BMI Photopolymerizable monomers EM2308 Photopolymerizable monomer produced by Changxing Materials Institute, product number EM2308 solvent NEP N-Ethylpyrrolidone

[0072] It should be noted that the hardened films of the above embodiments and comparative examples were prepared by the following steps: the prepared photosensitive resin composition was uniformly coated onto a glass substrate or copper substrate using a spin coater, and dried by pre-baking (pre-baking at 80°C to 120°C for 1 to 5 minutes) to prepare a pre-baked film with a thickness of 3 μm to 20 μm. Next, using a stepper exposure machine, ultraviolet light (wavelength of 300 nm to 500 nm, exposure amount of 200 mJ to 1000 mJ) was directly or through a photomask irradiated onto the pre-baked film. After exposure, the unexposed areas were dissolved and removed using a developer (cyclopentanone) to obtain a patterned resin film. The resin film was then placed in a deoxygenated oven for curing at a curing temperature of 170°C to 200°C for 1 to 3 hours to obtain a hardened film.

[0073] <Test of Hardened Film Properties>

[0074] The cyclization rate, chemical resistance and thermal properties of the hardened films of Examples 1 to 10 and Comparative Examples 1 to 4 will be tested below.

[0075] In the cyclization rate test, the hardened film is detected by a Fourier transform-infrared spectroscope (FT-IR), and the cyclization rate of the hardened film is calculated by the following formula: Cycloning rate = [(1-T% 1377) / (1-T% 1488)] / [(1-T% 1377) / (1-T% 1488)] @350°C; where T% 1377 and T% 1488 are the transmittance of FT-IR at wavelengths of 1377 nm and 1488 nm, respectively.

[0076] In the chemical resistance test, the hardened film was immersed in SPR920 solution (a chemical solution produced by Kanto Shinrin Group, consisting of tetramethylammonium hydroxide; TMAH, dimethyl sulfoxide DMSO and water) at 50°C, and the dissolution rate of the hardened film was measured.

[0077] In the thermal property tests, the thermogravimetric loss temperature (Td 5%) of the hardened film was measured using a thermogravimetric analyzer (TGA). The TGA instrument was a TA Instrument Q-500, and the test conditions were: nitrogen as the ambient gas, a heating rate of 10 °C / min, and a temperature increase from 40 °C to 500 °C. Furthermore, the storage modulus (E') and glass transition temperature (Tg) of the hardened film were measured using a dynamic mechanical analyzer (DMA). The DMA instrument was a Perkin Elmer DMA800, and the test conditions were: frequency 1 Hz, deformation 0.02 mm, a heating rate of 5 °C / min, and a temperature increase from 40 °C to 300 °C.

[0078] The test results of the hardened film properties of Examples 1 to 10 and Comparative Examples 1 to 4 are listed in Table 6 below: Table 6 cyclization rate Chemical resistance Td 5% E' (245°C) T g Example 1 A B A B B Example 2 A B A A A Example 3 A B A A A Example 4 A A A A A Example 5 A A A A A Example 6 A A A A A Example 7 A A A A A Example 8 A A A+ A A Example 9 B A B A B Example 10 B A B A B Comparative Example 1 A B A D D Comparative Example 2 A B B D D Comparative Example 3 D D E D D Comparative Example 4 D D E A A Evaluation criteria A: More than 90% B: 80% or more but less than 90% C: 70% or more but less than 80% D: 60% or more but less than 70% A: Dissolution rate is less than 30 nm / min B: Dissolution rate greater than 30 nm / min and less than 60 nm / min C: Dissolution rate greater than 60 nm / min and less than 100 nm / min D: Dissolution rate greater than 100 nm / min A+: Above 350°C A: Above 340°C and below 350°C B: Above 330°C and below 340°C C: Above 320°C and below 330°C D: Above 310°C and below 320°C E: Less than 310°C A: 0.4 GPa or more B: Above 0.2 GPa and below 0.4 GPa C: Above 0.1 GPa and less than 0.2 GPa D: Less than 0.1 GPa A: Above 260°C B: Above 250°C and below 260°C C: Above 240°C and below 250°C D: Less than 240°C

[0079] As can be seen from the results in Table 6 above, compared with the curing films of Comparative Examples 1 to 4, the curing film of the present disclosure can simultaneously possess higher cyclization rate, thermogravimetric loss temperature, storage modulus, glass transition temperature and better chemical resistance. Furthermore, in conjunction with the aforementioned Tables 3-2 and 4-2, it can be seen that the curing film of the present disclosure can possess the above-mentioned excellent material properties at a lower curing temperature (less than or equal to 200°C).

[0080] In summary, the photosensitive resin composition disclosed herein possesses a specific structure that facilitates polymer rearrangement and crosslinking reactions, and increases the crosslinking density of the polymer's polymer chains. Therefore, it maintains a high glass transfer temperature even at low-temperature baking temperatures (≤ 200°C), enhancing the thermal and mechanical properties of the cured product. Furthermore, the addition of a thermal alkali generator ensures high cyclization rates and good chemical resistance even at low-temperature processes (≤ 200°C). In addition, the photosensitive crosslinking groups in the polymer provide photosensitivity, allowing for patterning through exposure and development. Thus, the photosensitive resin composition simultaneously possesses the properties of both insulating and photoresistive materials, helping to reduce process steps, lower costs, and improve yield.

[0081] Although the present disclosure has been disclosed above by way of embodiments, it is not intended to limit the present disclosure. Any person skilled in the art may make various modifications and alterations without departing from the spirit and scope of the present disclosure. Therefore, the scope of protection of the present disclosure shall be determined by the appended claims. [Simplified Explanation of the Diagram]

[0082] None

Claims

1. A photosensitive resin composition comprising: a polymer having a plurality of repeating units as shown in formula (I) and a plurality of repeating units as shown in formula (II): Formula (I), Equation (II); in, A is a tetravalent organogroup with 6 to 40 carbon atoms, B1 and B2 are each independently a divalent organogroup with 6 to 40 carbon atoms, C is a trivalent to hexavalent organogroup containing 1 to 4 benzene rings, R1 is a photosensitive crosslinking group, and R2 has a structure as shown in formula (II-a) or formula (II-b): Formula (II-a), Equation (II-b); Wherein, R0 is a hydrogen atom or a methyl group, and X is an exomethyl group, an oxygen atom, or a sulfur atom; wherein, n is an integer from 1 to 150, m is an integer from 1 to 150, and y is an integer from 1 to 3; wherein, the repeating units shown in formula (I) are formed by reacting a dianhydride compound and a diamine compound, and the repeating units shown in formula (II) are formed by reacting a diacid compound and a diamine compound, wherein the diamine compound in formula (I) comprises at least one of an aromatic diamine and an alicyclic diamine, the dianhydride compound comprises at least one of an aromatic dianhydride and an alicyclic dianhydride, and the diamine compound in formula (II) comprises at least one of an aromatic diamine and an alicyclic diamine; wherein, when X is an exomethyl group, the following condition is satisfied: 0.1 ≤ the molar ratio of the repeating units shown in formula (II) to all repeating units of the polymer ≤ 0.

4.

2. A photosensitive resin composition comprising: a thermal alkali generating agent; and a polymer having a plurality of repeating units as shown in formula (I) and a plurality of repeating units as shown in formula (II): Formula (I), Equation (II); in, A is a tetravalent organogroup with 6 to 40 carbon atoms, B1 and B2 are each independently a divalent organogroup with 6 to 40 carbon atoms, C is a trivalent to hexavalent organogroup containing 1 to 4 benzene rings, R1 is a photosensitive crosslinking group, and R2 has a structure as shown in formula (II-a) or formula (II-b): Formula (II-a), Equation (II-b); Wherein, R0 is a hydrogen atom or a methyl group, and X is an enylmethyl group, an oxygen atom, or a sulfur atom; wherein, n is an integer from 1 to 150, m is an integer from 1 to 150, and y is an integer from 1 to 3; wherein, the repeating units shown in formula (I) are formed by the reaction of a dianhydride compound and a diamine compound, and the repeating units shown in formula (II) are formed by the reaction of a dianhydride compound and a diamine compound, wherein the diamine compound in formula (I) comprises at least one of an aromatic diamine and an alicyclic diamine, the dianhydride compound comprises at least one of an aromatic dianhydride and an alicyclic dianhydride, and the diamine compound in formula (II) comprises at least one of an aromatic diamine and an alicyclic diamine.

3. The photosensitive resin composition as claimed in claim 1 or claim 2, wherein A is a tetravalent organic group comprising 1 to 4 benzene rings, and B1 and B2 are each independently a divalent organic group comprising 1 to 4 benzene rings.

4. The photosensitive resin composition of claim 3, wherein at least one of the benzene rings of A, B1, B2 and C has at least one linker, and the at least one linker is a divalent organic group having 1 to 6 carbon atoms.

5. The photosensitive resin composition of claim 4, wherein the at least one linker comprises at least one selected from the group consisting of oxygen, nitrogen, sulfur, alkenyl, alkynyl, ester, ether, and ketone groups.

6. The photosensitive resin composition as claimed in claim 1 or claim 2, wherein R1 has a structure as shown in formula (III): Equation (III); in, R3 is an alkyl group having 1 to 8 carbon atoms, and R4 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

7. The photosensitive resin composition as claimed in claim 1 or claim 2 further comprises a thermal crosslinking agent.

8. The photosensitive resin composition of claim 7, wherein the thermal crosslinking agent has a thermally reactive functional group, and the thermally reactive functional group is selected from at least one of the group consisting of hydroxymethyl, alkoxymethyl, ethylene oxide, isocyanate, bismaleimino, alkenyl, and alkynyl.

9. The photosensitive resin composition as claimed in claim 1 or claim 2 further comprises at least one of a photoinitiator and a multifunctional acrylic photocrosslinker.

10. The photosensitive resin composition of claim 2, wherein the thermal alkali generating agent has at least one of a structure shown in formula (IV) and a structure shown in formula (V): Formula (IV), Formula (V); in, R5, R6, R7, R8, R9 and R10 are each independently a hydrogen atom, an aromatic cycloalkane or an alkyl group, and R11 is an alkylene group.

11. The photosensitive resin composition of claim 10, wherein at least one of R5, R6, R7, R8, R9, R10 and R11 is substituted with at least one selected from the group consisting of oxygen atom, nitrogen atom, sulfur atom, alkenyl group, alkynyl group, ether group and ketone group.

12. The photosensitive resin composition of claim 2, wherein the thermal alkali generating agent has at least one of a structure shown in formula (IV) and a structure shown in formula (V): Formula (IV), Formula (V); in, R5 is bonded to at least one of R6, R7 to R8, R9 to R10, and R9 to R11 to form a ring structure.

13. The photosensitive resin composition as claimed in claim 1 or claim 2, wherein the polymer is a copolymer.

14. A hardened film, which is cured from a photosensitive resin composition as described in claim 1 or claim 2; wherein, The repeating units shown in formula (I) in the photosensitive resin composition are cyclized to form a plurality of repeating units shown in formula (I-1): Formula (I-1).

15. The hardened membrane as claimed in claim 14, wherein the cyclization rate of the hardened membrane is 80% or more.