Photosensitive resin composition and hardened film

Abstract

One embodiment of the present disclosure provides a photosensitive resin composition comprising a polymer having a plurality of repeating units of Formula (I) and a plurality of repeating units of Formula (II), wherein each symbol in Formula (I) and Formula (II) is as defined in the specification. Accordingly, the photosensitive resin composition has a specific structure, which can improve the thermal properties, mechanical properties, and chemical resistance of the finished product after curing.

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. Background Technology

[0002] Polyimide is a polymer material with an imide 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 today's semiconductor manufacturing process.

[0003] Conventional polyimide precursors require high-temperature baking to obtain polyimide polymers, with baking temperatures reaching 230°C. Up to 350 This process ensures that the polyimide has a high glass transition temperature, good mechanical properties, and chemical resistance. However, high-temperature baking can easily lead to residual stress on the substrate supporting 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):

[0006]

[0007] Where A is a tetravalent organogroup with 6 to 40 carbon atoms, and B... 1 With B 2 Each is an independent divalent organogroup with 6 to 40 carbon atoms, and C is a trivalent to hexavalent organogroup with 6 to 40 carbon atoms. 1 It is a photosensitive crosslinking group, and R 2 It has a structure as shown in formula (II-a) or formula (II-b):

[0008]

[0009] Among them, R 0X is a hydrogen atom or a methyl atom, and X is a methylene atom, 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 a methylene atom, 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.

[0010] 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):

[0011]

[0012] Where A is a tetravalent organogroup with 6 to 40 carbon atoms, and B... 1 With B 2 Each is an independent divalent organogroup with 6 to 40 carbon atoms, and C is a trivalent to hexavalent organogroup with 6 to 40 carbon atoms. 1 It is a photosensitive crosslinking group, and R 2 It has a structure as shown in formula (II-a) or formula (II-b):

[0013]

[0014] Among them, R 0 X is a hydrogen atom or a methyl atom, and X is a methylene atom, 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.

[0015] According to the aforementioned photosensitive resin composition, A may be a tetravalent organic group containing 1 to 4 benzene rings, and B... 1 With B 2 Each can be an independent divalent organogroup containing 1 to 4 benzene rings, and C can be a trivalent to hexavalent organogroup containing 1 to 4 benzene rings.

[0016] According to the aforementioned photosensitive resin composition, wherein A and B 1 B 2 There may be at least one linker between the benzene ring and at least one of the C atoms, and the linker may be a divalent organic group having 1 to 6 carbon atoms.

[0017] 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.

[0018] According to the aforementioned photosensitive resin composition, wherein R 1 It can have a structure as shown in equation (III):

[0019]

[0020] Among them, R 3 It can be an alkylene group having 1 to 8 carbon atoms, and R 4 It can be a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0021] According to the aforementioned photosensitive resin composition, n can be an integer from 1 to 150, and m can be an integer from 1 to 150.

[0022] The aforementioned photosensitive resin composition may further include a thermal crosslinking agent.

[0023] 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, bismaleimide, alkenyl and alkynyl.

[0024] The aforementioned photosensitive resin composition may further include at least one of a photoinitiator and a polyfunctional acrylic photocrosslinker.

[0025] According to the aforementioned photosensitive resin composition, the thermal alkali generating agent may have at least one of the structures shown in formula (IV) and formula (V):

[0026]

[0027] Among them, R 5 R 6 R 7 R 8 R 9 With R 10 Each can be independently a hydrogen atom, an aromatic cyclic group, or an alkyl group, and R 11 It can be an alkylene group.

[0028] According to the aforementioned photosensitive resin composition, wherein R 5 R 6 R 7 R 8 R 9 R 10 With R 11 At least one of them may be replaced by at least one of the group consisting of oxygen atom, nitrogen atom, sulfur atom, alkenyl group, alkynyl group, ether group and ketone group.

[0029] According to the aforementioned photosensitive resin composition, the thermal alkali generating agent may have at least one of the structures shown in formula (IV) and formula (V):

[0030]

[0031] Among them, R 5 With R 6 R 7 With R 8 R 9 With R 10 and R 9 With R 11 At least one of them can be bonded to form a ring structure.

[0032] According to the aforementioned photosensitive resin composition, the polymer may be a copolymer.

[0033] Another embodiment of this disclosure provides a curing 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):

[0034] .

[0035] Based on the aforementioned hardened membrane, the cyclization rate of the hardened membrane can be above 80%.

[0036] Accordingly, the photosensitive resin composition of this disclosure has a specific structure that facilitates polymer rearrangement and crosslinking reactions, and increases the crosslinking density of the polymer's polymer chains. Therefore, it is suitable for low-temperature baking (≤200°C). It still has a high glass transition temperature, which improves the thermal and mechanical properties of the cured product. On the other hand, by adding a heat-alkali generating agent, it can achieve high glass transition temperature even in low-temperature processes (≤200). It retains a high cyclization rate and good chemical resistance even under these conditions. In addition, the photosensitive crosslinking groups in the polymer provide photosensitivity, so it can be patterned by 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. Detailed Implementation

[0037] The various embodiments of this disclosure will be discussed in further detail below. However, these embodiments may be applications of various disclosed concepts and may be implemented in various specific contexts. Specific embodiments are for illustrative purposes only and are not limited to the scope of the disclosure.

[0038] In this disclosure, compound structures are sometimes represented using a skeleton formula, which may omit carbon atoms, hydrogen atoms, and carbon-hydrogen bonds. If a functional group is explicitly shown in the structural formula, the formula shown shall prevail.

[0039] 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):

[0040]

[0041] Where A is a tetravalent organogroup with 6 to 40 carbon atoms, and B... 1 With B 2 Each is an independent divalent organogroup with 6 to 40 carbon atoms, and C is a trivalent to hexavalent organogroup with 6 to 40 carbon atoms. 1 It is a photosensitive crosslinking group, and R 2 It has a structure as shown in formula (II-a) or formula (II-b):

[0042]

[0043] Among them, R 0 X is a hydrogen atom or a methyl group, and X is a methylene, oxygen, or 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 a methylene 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, it will improve the thermal properties of the photosensitive resin composition, such as the storage modulus (E') or the glass transition temperature (T). g The effect of ) is quite significant, and after exposure, it is easier to cross-link and produce development contrast.

[0044] In detail, the multiple repeating units shown in formula (I) are formed by the reaction of a dianhydride compound and a diamine compound, and the multiple repeating units shown in formula (II) are formed by the reaction of a dianhydride compound and a diamine compound. The dianhydride compound may contain multiple 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).

[0045]

[0046] Alicyclic dianhydrides can be selected from at least one of the groups consisting of free formula (g), formula (h), and formula (i):

[0047]

[0048] 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.

[0049] The diamine compound may comprise a plurality of diamine monomers, and the diamine monomers may comprise at least one of aromatic diamines and alicyclic diamines. The aromatic diamines may be selected from at least one of the group consisting of free formulas (j), (k), (l), (m), (n), (o), (p), (q), (r), (s), (t), (u), (v), and (w).

[0050]

[0051] Alicyclic diamines can have structures such as those shown in formula (x):

[0052] .

[0053] 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):

[0054]

[0055] Where A is a tetravalent organogroup with 6 to 40 carbon atoms, and B... 1 With B 2 Each is an independent divalent organogroup with 6 to 40 carbon atoms, and C is a trivalent to hexavalent organogroup with 6 to 40 carbon atoms. 1 It is a photosensitive crosslinking group, and R 2 It has a structure as shown in formula (II-a) or formula (II-b):

[0056]

[0057] Among them, R 0 X is a hydrogen atom or a methyl atom, and X is a methylene atom, 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.

[0058] 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 comprising 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.

[0059] Accordingly, since the polymer in the photosensitive resin composition of this disclosure has a structure as shown in formula (II-a) or (II-b), it facilitates polymer rearrangement and crosslinking reactions 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 possesses good thermal properties (such as storage modulus or weight loss) and mechanical properties. On the other hand, by adding a heat-generating alkali agent, it is possible to achieve high glass transition temperatures at low temperatures (≤200°C). It retains a high cyclization rate and good chemical resistance even under these conditions. In addition, the photosensitive crosslinking groups in the polymer provide photosensitivity, so it can be patterned by 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.

[0060] Furthermore, A can be a tetravalent organogroup containing 1 to 4 benzene rings, and B... 1 With B 2 Each of A and B can be an independent divalent organogroup containing 1 to 4 benzene rings, and C can be a trivalent to hexavalent organogroup containing 1 to 4 benzene rings. 1 B 2 There may be at least one linker group between the benzene ring and at least one of the C atoms, and the linker group may be a divalent organic group having 1 to 6 carbon atoms. The linker group may include at least one of the group consisting of oxygen atom, nitrogen atom, sulfur atom, alkenyl, alkynyl, ester, ether and ketone groups.

[0061] Furthermore, R 1 It can have a structure as shown in equation (III):

[0062]

[0063] Among them, R 3 It can be an alkylene group having 1 to 8 carbon atoms, and R 4 It can be a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0064] Furthermore, n can be an integer from 1 to 150, and m can be an integer from 1 to 150.

[0065] Furthermore, the weight-average molecular weight (Mw) of the polymer can be between 10,000 and 50,000, and preferably between 20,000 and 40,000. Controlling the weight-average molecular weight of the polymer is beneficial for the formation of patterns.

[0066] 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 hydroxymethyl ( ), alkoxymethyl ( The composition comprises at least one of the groups consisting of ethylene oxide, isocyanate group, bismaleimide group, alkenyl group, and alkynyl group, wherein R may be an alkyl group, preferably an alkyl group having 1 to 3 carbon atoms, but not limited thereto. The thermal crosslinking agent accounts for 0.1% to 20% of the photosensitive resin composition, preferably 0.1% to 10%, and more preferably 3% to 5%. Furthermore, the crosslinking temperature of the thermal crosslinking agent may be 120°C. Up to 170 .

[0067] The photosensitive resin composition may further include at least one of a photoinitiator and a polyfunctional acrylic photocrosslinker, which helps to promote the photocuring reaction of the photosensitive resin composition. The photoinitiator may be selected from free acylphosphine oxide compounds, transition metal compounds, oxime compounds, benzophenone derivatives, etc. -Hydroxyketone compounds and At least one of the group consisting of aminoalkylbenzophenone compounds. The photoinitiator may account for 0.1% to 5% of the photosensitive resin composition.

[0068] The thermal alkali generating agent can generate alkaline substances during heating in a low-temperature process to promote the ring-closure reaction of the photosensitive resin composition. Another embodiment of this disclosure provides a thermal alkali generating agent that may have at least one of the structures shown in formula (IV) and formula (V):

[0069]

[0070] Among them, R 5 R 6 R 7 R 8 R 9 With R 10 Each can be independently a hydrogen atom, an aromatic cyclic group, or an alkyl group, and R 11 It can be an alkylene group. Furthermore, R... 5 R 6 R 7 R 8 R 9 R 10 With R 11 At least one of them may be substituted 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. Furthermore, R 5 With R 6 R 7 With R 8 R 9 With R 10 and R 9 With R 11At least one of them can be bonded to form a ring structure.

[0071] 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 100°C. Up to 170 The acid dissociation constant (pKa) of the conjugate acid of a basic substance can be greater than 5.

[0072] 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 cations and anions. The cations can be selected from the group consisting of primary amines, secondary amines, tertiary amines, amidine, and guanidine, and the anions can include organic acid anions or inorganic acid anions, or the anions can be selected from the group consisting of carboxylate anions, sulfate anions, phosphate anions, and phenols.

[0073] 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%.

[0074] In another embodiment of this disclosure, the photosensitive resin composition may further include a solvent, including but not limited to: The solvent, consisting of butyrolactone, N-methylpyrrolidone, dimethyl sulfoxide, N-ethylpyrrolidone, dimethylformamide, or dimethylacetamide, preferably accounts for 30% to 80% of the photosensitive resin composition.

[0075] In another embodiment of this disclosure, the photosensitive resin composition may further include other additives, such as at least one of leveling agents, heterogeneous interface promoters, sensitizers, and antioxidants, to improve the processability, stability, and finished product characteristics of the photosensitive resin composition.

[0076] Another embodiment of this disclosure provides a curing 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):

[0077] .

[0078] Furthermore, the cyclization rate of the hardened film can be over 80%, thus the aforementioned photosensitive resin composition can possess excellent cyclization characteristics during curing.

[0079] The following specific embodiments further illustrate the content of this disclosure, so that those skilled in the art to which this disclosure pertains can fully utilize and practice the content of this disclosure without excessive interpretation. These embodiments should not be regarded as limiting the scope of this disclosure, but rather as materials and methods for illustrating how to implement the content of this disclosure.

[0080] <Synthesis Examples>

[0081] Synthesis Example 1: In a 1L three-necked flask, ODPA (55mmol; 17.1g), PMDA (30mmol; 6.5g), HEMA (170mmol; 22.1g), pyridine (170mmol; 13.5g), and GBL (200g) were added, and the mixture was heated to 60°C. After stirring for 2 hours, the mixture was cooled in an ice bath. Then, a diacid compound (15 mmol; 4.9 g) as shown in formula (II-b-1) was added. Subsequently, 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 through a feed tube. The resulting reaction mixture was stirred in an ice bath for 18 hours. After filtering to remove the precipitate, the resulting reaction solution was added dropwise to 4 L of water. The solid was then filtered, separated, and vacuum dried to obtain the polymer of Example 1. The molar ratio of the repeating unit as shown in formula (II) to all repeating units of the polymer in Example 1 was calculated to be 0.15.

[0082] The weight-average molecular weight of the polymer was determined by gel permeation chromatography (GPC) using standard polystyrene as a calibrator. The weight-average molecular weight of the polymer synthesized in Example 1 was 28,500.

[0083] Furthermore, the reactants of Synthetic Example 1 can undergo the chemical reaction shown in Formula (A) to obtain the polymer of Synthetic Example 1:

[0084] .

[0085] 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, and then sodium acetate (135 mmol; 11.1 g) and acetic anhydride (1.5 mol; 153 g) are added. The mixture is stirred at 60 °C. After stirring for 2 hours, the mixture was cooled to room temperature and poured into 2L of dilute hydrochloric acid (1M). The resulting solid was then filtered and separated, and after vacuum drying, it became the dicarboxylic acid compound shown in formula (II-b-1).

[0086] It should be noted that A, X, and B in equation (A) 1 B 2 With R 1 The chemical structures of the functional groups can vary 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 from ODPA or PMDA, and the diamine compound used in Synthesis Example 1 is mMEA and m-tolidine, therefore the H2N-B group in formula (A) can be any aromatic group from ODPA or PMDA. 1 -N2H can be either mMEA or m-tolidine, and H2N-B 2 -N2H can also be arbitrarily mMEA or m-tolidine, that is, in the polymer structure shown in formula (A), A and B 1 With B 2 The functional groups are not limited to a specific structure and can be any combination of the dianhydride and diamine compounds used. Furthermore, the reaction mechanisms of the 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.

[0087] Synthesis Example 2: The synthesis steps of the polymer in Synthesis Example 2 were the same as those in Synthesis Example 1, except that the reactants used in Synthesis 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), a 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 molar ratio of the repeating unit as shown in Formula (II) to all repeating units of the polymer in Synthetic Example 2 is calculated to be 0.30.

[0088] 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 molar ratio of the repeating unit as shown in Formula (II) to all repeating units of the polymer in Synthetic Example 3 is calculated to be 0.20.

[0089] 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), except that Nadic anhydride needs to be replaced with 3,6-oxo-1,2,3,6-tetrahydrophthalic anhydride.

[0090] Synthesis Example 4: The synthesis steps of the polymer in Synthesis Example 4 were the same as those in Synthesis Example 1, except that the reactants used in Synthesis Example 4 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 (81 mmol; 17.2 g of m-tolidine dissolved in 150 g of GBL). In Synthesis Example 4, the mMEA solution was replaced with an ODA solution (20 mmol; 4 g of ODA dissolved in 50 g of GBL), 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 4 has a weight-average molecular weight of 19,700, wherein the molar ratio of the repeating unit as shown in Formula (II) to all repeating units of the polymer in Synthetic Example 4 is calculated to be 0.30.

[0091] Synthesis Example 5: The synthesis steps of the polymer in Synthesis Example 5 were the same as those in Synthesis Example 1, except that the reactants used in Synthesis Example 5 were 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 molar ratio of the repeating unit as shown in Formula (II) to all repeating units of the polymer in Synthetic Example 5 is calculated to be 0.30.

[0092] 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). Furthermore, mMEA solution was not used in Synthesis Example 6, and 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 molar ratio of the repeating unit as shown in Formula (II) to all repeating units of the polymer in Synthetic Example 6 is calculated to be 0.15.

[0093] 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), except that 5-aminoisophthalic acid needs to be replaced with bis(4-amino-3-carboxyphenyl)methane.

[0094] 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 molar ratio of the repeating unit as shown in Formula (II) to all repeating units of the polymer in Synthetic Example 7 is calculated to be 0.30.

[0095] 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), except that nadic anhydride needs to be replaced with methylmaleic anhydride.

[0096] <Comparative Example of Synthesis>

[0097] 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.

[0098] 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 molar ratio of the repeating unit as shown in Formula (II) to all repeating units of the polymer in Comparative Example 2 is calculated to be 0.3.

[0099] Comparative Example 3: The synthesis steps of the polymer in Comparative Example 3 were the same as those in Comparative Example 1, except that 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). Furthermore, Comparative Example 3 did not use PMDA and m-tolidine solution, and the mMEA solution was replaced with ODA solution (103 mmol; 20.6 g of ODA dissolved in 200 g of GBL). The weight-average molecular weight of the polymer in Comparative Example 3 was 37,900. The calculated molar ratio of the repeating unit as shown in formula (II) to all repeating units in the polymer of Comparative Example 3 was 0.05.

[0100] 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 weight-average molecular weight of the polymer in Comparative Example 4 was 20,000, and the molar ratio of the repeating unit as shown in formula (II) to all repeating units in the polymer in Comparative Example 4 was calculated to be 0.5.

[0101] The reactants used in the above synthetic examples and comparative examples are listed in Table 1 below, and the diacid compounds and their chemical structures are listed in Table 2 below:

[0102]

[0103]

[0104] <Example>

[0105] The hardened films of Examples 1 to 10 were obtained by preparing photosensitive resin compositions from the polymers synthesized in Examples 1 to 7 according to the component ratios in Tables 3-1 and 3-2 below, followed by curing.

[0106]

[0107]

[0108] <Comparative Example>

[0109] The hardened films of Comparative Examples 1 to 4 were obtained by preparing photosensitive resin compositions using the polymers synthesized in Comparative Examples 1 to 4 according to the component ratios in Tables 4-1 and 4-2 below, followed by curing.

[0110]

[0111]

[0112] The ingredients used in the above embodiments and comparative examples are listed in Table 5 below:

[0113]

[0114]

[0115] 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 then pre-baked (80°C). Up to 120 Pre-baking for 1 to 5 minutes allows the film to dry, resulting in a pre-baked film with a thickness of 3 μm to 20 μm. Next, using a stepper exposure machine, ultraviolet light (wavelength 300 nm to 500 nm, exposure dose 200 mJ to 1000 mJ) is applied directly or via a photomask to the pre-baked film. After exposure, the unexposed areas are dissolved and removed using a developer (cyclopentanone) to obtain a patterned resin film. The resin film is then placed in a deoxygenated oven for curing at 170°C. Up to 200 The baking time is 1 to 3 hours to obtain a hardened film.

[0116] <Hardened Film Property Test>

[0117] 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.

[0118] In the cyclization rate test, the hardened film was detected using a Fourier transform-infrared spectrometer (FT-IR), and the cyclization rate of the hardened film was calculated using the following formula:

[0119] Cycloning rate = [(1-T%] 1377 ) / (1-T% 1488 )] / [(1-T% 1377 ) / (1-T% 1488 )] @350 ;

[0120] Among them, T% 1377 With T% 1488 The transmittance of FT-IR at wavelengths of 1377 nm and 1488 nm are respectively.

[0121] In the chemical resistance test, the hardened film is immersed in 50... The solution was prepared in SPR920 solution (a chemical solution produced by Kanto Shinrin Group, consisting of tetramethylammonium hydroxide, TMAH, dimethyl sulfoxide (DMSO), and water), and the dissolution rate of the hardened film was measured.

[0122] In thermal property testing, the thermogravimetric analyzer (TGA) is used to detect the thermogravimetric loss temperature (Td) of the hardened film. 5% The TGA testing instrument was a TA Instrument Q-500, and the testing conditions were nitrogen as the ambient gas and a heating rate of 10°C. o C / min, from 40 o C rises to 500 o C. Furthermore, the storage modulus (E') and glass transition temperature (T) of the hardened film were determined using a dynamic mechanical analyzer (DMA). g The DMA testing instrument was a Perkin Elmer DMA800, and the test conditions were: frequency 1 Hz, deformation 0.02 mm, and heating rate 5. o C / min, from 40 o C rises to 300 o C.

[0123] 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:

[0124]

[0125]

[0126]

[0127] As can be seen from the results in Table 6 above, compared with the cured films of Comparative Examples 1 to 4, the cured film of this 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 at a lower curing temperature (less than or equal to 200°C), the cured film can achieve better performance. The hardened film of this disclosure can possess the aforementioned excellent material properties.

[0128] In summary, the photosensitive resin composition of this disclosure has a specific structure that facilitates polymer rearrangement and crosslinking reactions, and increases the crosslinking density of the polymer's polymer chains. Therefore, it is suitable for low-temperature baking (≤200°C). It still has a high glass transition temperature, which improves the thermal and mechanical properties of the cured product. On the other hand, by adding a heat-alkali generating agent, it can achieve high glass transition temperature even in low-temperature processes (≤200). It retains a high cyclization rate and good chemical resistance even under these conditions. In addition, the photosensitive crosslinking groups in the polymer provide photosensitivity, so it can be patterned by 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.

[0129] Although the present disclosure has been described above with reference to 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.

Claims

1. A photosensitive resin composition comprising: Polymers having multiple repeating units as shown in formula (I) and multiple repeating units as shown in formula (II): in, A is a tetravalent organic group with 6 to 40 carbon atoms, B 1 With B 2 Each is an independent divalent organogroup with 6 to 40 carbon atoms, and C is a trivalent to hexavalent organogroup with 6 to 40 carbon atoms. 1 It is a photosensitive crosslinking group, and R 2 It has a structure as shown in formula (II-a) or formula (II-b): Among them, R 0 X is a hydrogen atom or a methyl atom, and X is a methylene atom, an oxygen atom, or a sulfur atom; Where 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; Wherein, when X is methylene, the following condition is satisfied: 0.1 ≤ the molar ratio of these repeating units as shown in formula (II) to all repeating units of the polymer ≤ 0.

4.

2. A photosensitive resin composition comprising: Heat-generating alkali agents; and Polymers having multiple repeating units as shown in formula (I) and multiple repeating units as shown in formula (II): in, A is a tetravalent organic group with 6 to 40 carbon atoms, B 1 With B 2 Each is an independent divalent organogroup with 6 to 40 carbon atoms, and C is a trivalent to hexavalent organogroup with 6 to 40 carbon atoms. 1 It is a photosensitive crosslinking group, and R 2 It has a structure as shown in formula (II-a) or formula (II-b): Among them, R 0 X is a hydrogen atom or a methyl atom, and X is a methylene atom, an oxygen atom, or a sulfur atom; Where 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.

3. The photosensitive resin composition of claim 1 or claim 2, wherein A is a tetravalent organic group comprising 1 to 4 benzene rings, and B... 1 With B 2 Each is an independent divalent organogroup containing 1 to 4 benzene rings, and C is a trivalent to hexavalent organogroup containing 1 to 4 benzene rings.

4. The photosensitive resin composition of claim 3, wherein A and B 1 B 2 The benzene ring of at least one of C has at least one linking group, and the at least one linking group is a divalent organic group having 1 to 6 carbons.

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 of claim 1 or claim 2, wherein R 1 It has the structure shown in equation (III): in, R 3 It is an alkylene group having 1 to 8 carbon atoms, and R 4 It consists of hydrogen atoms or alkyl groups having 1 to 3 carbon atoms.

7. The photosensitive resin composition of claim 1 or claim 2, wherein n is an integer from 1 to 150, and m is an integer from 1 to 150.

8. The photosensitive resin composition of claim 1 or claim 2, further comprising a thermal crosslinking agent.

9. The photosensitive resin composition of claim 8, 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, bismaleimide, alkenyl, and alkynyl.

10. The photosensitive resin composition of claim 1 or claim 2, further comprising at least one of a photoinitiator and a polyfunctional acrylic photocrosslinker.

11. The photosensitive resin composition of claim 2, wherein the thermal alkali generating agent has at least one of the structures shown in formula (IV) and formula (V): in, R 5 R 6 R 7 R 8 R 9 With R 10 Each is independently a hydrogen atom, an aromatic cyclic group, or an alkyl group, and R 11 It is an alkylene group.

12. The photosensitive resin composition of claim 11, wherein R 5 R 6 R 7 R 8 R 9 R 10 With R 11 At least one of them is replaced by at least one of the group consisting of oxygen atom, nitrogen atom, sulfur atom, alkenyl group, alkynyl group, ether group and ketone group.

13. The photosensitive resin composition of claim 2, wherein the thermal alkali generating agent has at least one of the structures shown in formula (IV) and formula (V): in, R 5 With R 6 R 7 With R 8 R 9 With R 10 and R 9 With R 11 At least one of them is bonded to form a ring structure.

14. The photosensitive resin composition of claim 1 or claim 2, wherein the polymer is a copolymer.

15. A hardened film, which is formed by curing the photosensitive resin composition as described in claim 1 or claim 2; in, In this photosensitive resin composition, the repeating units as shown in formula (I) undergo a cyclization reaction to form multiple repeating units as shown in formula (I-1): 。 16. The hardened membrane of claim 15, wherein the cyclization rate of the hardened membrane is 80% or more.

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