Alkali-soluble light-cured resin, preparation method thereof and light-cured resin composition

Abstract

The invention relates to alkali-soluble light-cured resin and a preparation method thereof, a light-cured resin composition, a photosensitive dry film and a semiconductor device. The structural formula of the alkali-soluble light-cured resin is shown as a formula (I) or a formula (II), wherein in the formula (I), R1 is selected from one of a single bond, an oxygen atom, a sulfonyl group and an organic group with 1-30 carbon atoms; in the formula (I) and the formula (II), n is a natural number greater than or equal to 0; r2 is selected from organic groups with 1-50 carbon atoms; r3 is selected from an aromatic organic group or an aliphatic organic group; r4 is selected from organic groups containing unsaturated carbon-carbon double bonds; and R5 is selected from carboxyl-containing organic groups. A molecular chain of the alkali-soluble light-cured resin contains a photosensitive group, an imide structure and an alkali-soluble group, on one hand, the thermal mechanical property of the alkali-soluble light-cured resin can be enhanced, and on the other hand, the alkali-soluble light-cured resin can form a uniform and stable resin glue solution in a solvent, so that the comprehensive performance of the alkali-soluble light-cured resin is improved.

Description

Technical Field

[0001] The present application relates to the technical field of resin compositions, and particularly relates to an alkali-soluble photocurable resin, a preparation method thereof, a photocurable resin composition, a photosensitive dry film, and a semiconductor device. Background Art

[0002] With the development of electronic products towards lightweight, miniaturization, and high performance, higher requirements are put forward for the solder mask covering the circuit. The solder mask not only needs to prevent the solder from flowing into the circuit during the soldering process, but also needs to be used as a plating protection layer during the plating process; in addition, the solder mask also needs to protect the circuit from moisture, dust, and chemicals during use, and reduce the stress generated during the bending process. Therefore, the solder mask needs to have excellent thermomechanical properties, flexibility, adhesion, and other properties.

[0003] An alkali-soluble photocurable resin is used as the main resin of the solder mask material. However, the thermomechanical properties of this resin after curing are still insufficient. In related technologies, a polyimide resin is added to the photocurable resin composition to improve the thermomechanical properties of the composition. However, there is a compatibility problem between the polyimide resin and the alkali-soluble photocurable resin. The added polyimide resin is insoluble in the alkali-soluble photocurable resin or phase separation occurs between the added polyimide resin and the alkali-soluble photocurable resin, resulting in unsatisfactory thermodynamic properties of the composite cured product. Summary of the Invention

[0004] Embodiments of the present application provide an alkali-soluble photocurable resin, a preparation method thereof, a photocurable resin composition, a photosensitive dry film, and a semiconductor device to at least partially solve the above technical problems.

[0005] To achieve the above object, according to the first aspect of the present application, an alkali-soluble photocurable resin is provided, and the structural formula of the alkali-soluble photocurable resin is shown in Formula (I) or Formula (II):

[0006]

[0007]

[0008] In Formula (I), R1 is selected from one of the following: a single bond, an oxygen atom, a sulfonyl group, and an organic group with 1 to 30 carbon atoms;

[0009] In Formula (I) and Formula (II), n is a natural number greater than or equal to 0; R2 is selected from an organic group with 1 to 50 carbon atoms; R3 is selected from an aromatic organic group or an aliphatic organic group; R4 is selected from an organic group containing an unsaturated carbon-carbon double bond; R5 is selected from an organic group containing a carboxyl group.

[0010] Optionally, in formula (I), R1 is selected from organic groups containing at least one of a halogen substituent, a carbonyl group, an ether group, a phenyl group, an ester group, and an alkynyl group.

[0011] Optionally, in formula (I), R1 is selected from one of the following groups:

[0012]

[0013]

[0014] where represents the connection point on the organic group.

[0015] Optionally, in formula (I) and formula (II), R2 is selected from organic groups containing at least one of a benzene ring, a siloxy group, an ether group, a heterocyclic nitrogen group, and a carboxyl group.

[0016] Optionally, in formula (I) and formula (II), R2 is selected from one of the following groups:

[0017]

[0018]

[0019]

[0020] where represents the connection point on the organic group.

[0021] Optionally, n is greater than or equal to 1 and less than or equal to 10.

[0022] Optionally, the number-average molecular weight of the following carbon structural unit in formula (I) is 500 g / mol to 5000 g / mol:

[0023] Or

[0024] the number-average molecular weight of the following carbon structural unit in formula (II) is 500 g / mol to 5000 g / mol:

[0025]

[0026] Optionally, the acid value of the alkali-soluble photocurable resin is 30 mg KOH / g to 200 mg KOH / g.

[0027] Optionally, the number-average molecular weight of the alkali-soluble photocurable resin is 5000 g / mol to 20000 g / mol.

[0028] According to the second aspect of the present application, there is provided a method for preparing an alkali-soluble photocurable resin, including:

[0029] Performing a polycondensation reaction on an acid anhydride monomer and a diamine monomer in a first solvent to obtain a polyamic acid, wherein the acid anhydride monomer includes a carboxylic acid anhydride monomer, and the polyamic acid is a carboxylic acid-terminated polyamic acid;

[0030] Performing a chemical imidization treatment on the carboxylic acid-terminated polyamic acid to obtain a carboxylic acid-terminated polyimide oligomer;

[0031] Performing an esterification reaction on the carboxylic acid-terminated polyimide oligomer and a polyfunctional epoxide to obtain a polyfunctional epoxide containing an imide structure;

[0032] Performing an esterification reaction on the polyfunctional epoxide containing an imide structure and an unsaturated carboxylic acid to obtain an esterified product;

[0033] Reacting the esterified product with a polybasic anhydride to obtain an alkali-soluble photocurable resin.

[0034] Optionally, the diamine monomer includes at least one of 4,4'-diaminodiphenyl ether, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, aminopropyl-terminated polydimethylsiloxane, 3,5-diamino-1,2,4-triazole, diaminopyridine, 2-(4-aminophenyl)-5-aminobenzimidazole, 2,2'-bis[4-(4-aminophenoxyphenyl)]propane, 6,6'-diamino-3,3'-methylenedibenzoic acid, 1H-indazole-4,7-diamine, 2,2'-diamino-4,4'-bithiazole, 3,6-diaminocarbazole, methyl 2-(3,6-diamino-9H-carbazol-9-yl)acetate, 2,5-diaminobenzothiazole, 2,6-benzothiazolediamine, tert-butyl (6-amino-4-methylbenzo[d]thiazol-2-yl)carbamate, 4-methoxy-1,3-benzothiazole-2,6-diamine, melamine, 2,4-diamino-6-(2-fluorophenyl)-1,3,5-triazine, 2,4-diamino-6-(4-chlorophenyl)-1,3,5-triazine, 2,4-diamino-6-[4-(trifluoromethyl)phenyl]-1,3,5-triazine, 2,4-diamino-6-(3-fluorophenyl)-1,3,5-triazine, 2,4-diamino-6-[3-(trifluoromethyl)phenyl]-1,3,5-triazine, 2,4-diamino-6-(4-methylphenyl)-1,3,5-triazine, 2,4-diamino-6-(3,5-difluorophenyl)-1,3,5-triazine, 2,4-diamino-6-(4-bromophenyl)-1,3,5-triazine, 2,4-diamino-6-(4-methoxyphenyl)-1,3,5-triazine, 2,3-diaminophenazine, methylguanamine, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine, and 4,6-diaminopyrimidine.

[0035] Optionally, the carboxylic anhydride monomer includes at least one of trimellitic anhydride and 1,3-dioxo-1,3-dihydroisobenzofuran-4-carboxylic acid.

[0036] Optionally, the molar ratio of the carboxylic anhydride monomer to the diamine monomer is 2 to 2.5:1.

[0037] Optionally, the polyfunctional epoxide includes polyfunctional epoxy resin, and the polyfunctional epoxy resin includes at least one of bisphenol A novolac epoxy resin, naphthalene epoxy resin, phenol novolac epoxy resin, glycidylamine epoxy resin, o-cresol novolac epoxy resin, alkylphenol novolac epoxy resin, dicyclopentadiene epoxy resin, tetraphenylethane epoxy resin, trihydroxybenzene methane epoxy resin, diglycidyl phthalate resin, and epoxy resin of the condensate of phenols and aromatic aldehydes having phenolic hydroxyl groups.

[0038] Optionally, the unsaturated carboxylic acid includes at least one of an unsaturated monocarboxylic acid and an unsaturated polycarboxylic acid.

[0039] Optionally, the polyanhydride includes at least one of a dianhydride, a polyaromatic carboxylic anhydride, and an acid anhydride derivative.

[0040] Optionally, when subjecting the carboxylic anhydride monomer and the diamine monomer to a polycondensation reaction, a dianhydride monomer is further added, such that the dianhydride monomer and the carboxylic anhydride monomer together undergo a polycondensation reaction with the diamine monomer.

[0041] Optionally, the dianhydride monomer includes at least one of pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-diphenylethertetracarboxylic dianhydride, 4,4'-oxybisphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3,4,4-diphenylsulfonetetracarboxylic dianhydride, 4,4'-phenylenedioxybisphthalic anhydride, hexafluorodiacid anhydride, 1,2-ethylenedi[1,3-dihydro-1,3-dioxoisobenzofuran-5-carboxylate], bisphenol A dianhydride, glycerol bis(tridecahydrophthalate) acetate, 2,3,3',4'-biphenyltetracarboxylic dianhydride, p-phenylene-bis(trimellitate) dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, and 4,4'-(ethyne-1,2-diyl)diphthalic anhydride.

[0042] According to a third aspect of the present application, there is provided a photocurable resin composition. By mass, the photocurable resin composition includes 100 parts of an alkali-soluble photocurable resin, 15 parts to 45 parts of a thermosetting resin, and 0.5 parts to 2 parts of a photoinitiator; the alkali-soluble photocurable resin is the alkali-soluble photocurable resin as described above or an alkali-soluble photocurable resin prepared by the preparation method of the alkali-soluble photocurable resin as described above.

[0043] Optionally, by mass, the photocurable resin composition further includes 5 parts to 15 parts of a photopolymerizable monomer.

[0044] Optionally, by mass, the photocurable resin composition further includes 10 parts to 80 parts of an inorganic filler.

[0045] Optionally, by mass, the photocurable resin composition further includes 2 parts to 10 parts of a curing agent.

[0046] Optionally, the photocurable resin composition further includes a second solvent.

[0047] According to a fourth aspect of the present application, a photosensitive dry film is provided, which comprises the photocurable resin composition as described above or a cured product of the photocurable resin composition prepared by the preparation method of the photocurable resin composition as described above.

[0048] According to a fifth aspect of the present application, a semiconductor device is provided, which comprises the photosensitive dry film as described above.

[0049] The molecular chain of the alkali-soluble photocurable resin provided by the embodiments of the present application contains an imide group (-C(O)-N(R)-C(O)-), that is, the molecular chain of the alkali-soluble photocurable resin contains an imide structure. At the same time, the molecular chain of the alkali-soluble photocurable resin also contains an unsaturated carbon-carbon double bond (-C=C-), which can be used as a photosensitive group; in addition, the molecular chain of the alkali-soluble photocurable resin also contains a carboxyl group (-COOH) and an ester group (-COO-), and these groups can be used as alkali-soluble groups. That is to say, the molecular chain of the alkali-soluble photocurable resin provided by the embodiments of the present application contains a photosensitive group, an alkali-soluble group and an imide structure at the same time. By directly introducing the imide structure into the molecular chain structure of the alkali-soluble photocurable resin, on the one hand, the thermomechanical properties of the alkali-soluble photocurable resin can be enhanced, and on the other hand, the alkali-soluble photocurable resin can form a homogeneous and stable resin solution in the solvent, thereby improving the comprehensive properties of the alkali-soluble photocurable resin.

[0050] Other features and advantages of the present application will be described in detail in the subsequent specific embodiments section. Description of the Drawings

[0051] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for the description of the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without creative efforts.

[0052] Figure 1 is the nuclear magnetic spectrum of the alkali-soluble photocurable resin prepared in Step 2 of Example 1 of the present application;

[0053] Figure 2 is the infrared spectrum of the alkali-soluble photocurable resin prepared in Step 2 of Example 1 of the present application. Detailed Description of the Embodiments

[0054] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present application without creative efforts shall fall within the protection scope of the present application.

[0055] According to the first aspect of the embodiments of the present application, the embodiments of the present application provide an alkali-soluble photocurable resin, and the structural formula of the alkali-soluble photocurable resin is shown in Formula (I) or Formula (II):

[0056]

[0057] In Formula (I), R1 is selected from one of the following: a single bond, an oxygen atom, a sulfonyl group, and an organic group with 1 to 30 carbon atoms; in Formula (I) and Formula (II), n is a natural number greater than or equal to 0; R2 is selected from an organic group with 1 to 50 carbon atoms; R3 is selected from an aromatic organic group or an aliphatic organic group; R4 is selected from an organic group containing an unsaturated carbon-carbon double bond; R5 is selected from an organic group containing a carboxyl group.

[0058] In Formula (I) and Formula (II), n is a natural number greater than or equal to 0. That is to say, n can be 0 or other positive integers greater than 0. It can be seen that when n = 0, neither of Formula (I) and Formula (II) contains the carbon structural unit within the curly brackets, and at this time, Formula (I) and Formula (II) are the same. When n is a positive integer greater than 0, Formula (I) and Formula (II) are different. It can be understood that the larger n is, the longer the molecular chain of the alkali-soluble photocurable resin is and the more complex the molecular structure of the alkali-soluble photocurable resin is.

[0059] It can be seen that when Formula (I) and Formula (II) are different, the difference between Formula (I) and Formula (II) is that Formula (I) contains R1 and Formula (II) does not contain R1.

[0060] In Formula (I), R1 is respectively connected to two benzene rings. When R1 is a single bond, the two benzene rings are connected together by a single bond; when R1 is an oxygen atom, the two benzene rings are connected together by an oxygen atom; when R1 is a sulfonyl group, the two benzene rings are connected together by a sulfonyl group, specifically, the two benzene rings are respectively connected to the sulfur atom on the sulfonyl group. As an example, the structure of the sulfonyl group is as follows:

[0061]

[0062] Where represents the connection point of the sulfonyl group.

[0063] R1 may also be selected from organic groups having 1 to 30 carbon atoms. The type of this organic group is not limited here. It may contain substituents or may not contain substituents. It may be a straight-chain structure, a branched-chain structure or a cyclic structure, and may be a saturated structure or an unsaturated structure. As an example, R1 is selected from organic groups having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30 carbon atoms.

[0064] Both formula (I) and formula (II) contain R2, R3, R4 and R5.

[0065] Specifically, R2 is selected from organic groups having 1 to 50 carbon atoms. The type of this organic group is not limited here either. It may contain substituents or may not contain substituents. It may be a straight-chain structure, a branched-chain structure or a cyclic structure, and may be a saturated structure or an unsaturated structure. As an example, R2 is selected from organic groups having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 or 50 carbon atoms.

[0066] R3 is selected from aromatic organic groups or aliphatic organic groups. That is to say, R3 may be an aromatic organic group. An aromatic organic group refers to a functional group derived from an aromatic ring, that is, a functional group formed after at least one H is removed from the aromatic ring. The aromatic ring may include a benzene ring and its derivatives (such as naphthalene, anthracene, etc.). R3 may also be an aliphatic organic group. An aliphatic organic group refers to a functional group derived from outside the aromatic ring. Aliphatic organic groups mainly contain carbon and hydrogen elements, and in addition may contain elements such as oxygen, nitrogen, sulfur, chlorine, etc. Aliphatic organic groups may be derived from various types of aliphatic organic compounds, including alkanes, alkenes, alcohols, ethers, ketones, aldehydes, esters, amines, etc. In addition, it should be noted here that aliphatic organic groups may be saturated organic groups or unsaturated organic groups; aliphatic organic groups may be open-chain structures or cyclic structures (non-aromatic rings).

[0067] R4 is selected from organic groups containing an unsaturated carbon-carbon double bond. That is to say, R4 contains an unsaturated carbon-carbon double bond (C=C).

[0068] R5 is selected from organic groups containing a carboxyl group. That is to say, R5 contains a carboxyl group (-COOH).

[0069] As can be seen from the above, the molecular chain of the alkali-soluble photocurable resin provided by the embodiments of the present application contains an imide group (-C(O)-N(R)-C(O)-), where R represents an organic group, that is, the molecular chain of the alkali-soluble photocurable resin contains an imide structure. At the same time, the molecular chain of the alkali-soluble photocurable resin also contains an unsaturated carbon-carbon double bond (-C=C-), which can serve as a photosensitive group; in addition, the molecular chain of the alkali-soluble photocurable resin also contains a carboxyl group (-COOH) and an ester group (-COO-), and these groups can serve as alkali-soluble groups. As an example, the carboxyl group can lose a proton to form a carboxylate salt under alkaline conditions, thereby showing alkali solubility.

[0070] That is to say, the molecular chain of the alkali-soluble photocurable resin provided by the embodiments of the present application contains a photosensitive group, an alkali-soluble group and an imide structure at the same time.

[0071] Specifically, a photosensitive group refers to a specific chemical group that can absorb light energy and initiate a chemical reaction. The molecular chain of the alkali-soluble photocurable resin contains a photosensitive group, and the photosensitive group can be used to make the alkali-soluble photocurable resin cure after being irradiated with light, that is, realize photocuring. An alkali-soluble group refers to a chemical group that can dissolve or react under alkaline conditions. The molecular chain of the alkali-soluble photocurable resin also contains an alkali-soluble group, and the alkali-soluble group can be used to make the alkali-soluble photocurable resin develop an image through alkaline water after photocuring, so as to realize pattern transfer and etching.

[0072] The traditional alkali-soluble photocurable resin only contains a photosensitive group and an alkali-soluble group. In the embodiments of the present application, the traditional alkali-soluble photocurable resin is chemically modified, and an imide structure is further introduced into the molecular chain of the alkali-soluble photocurable resin. The imide structure refers to a carbon structural unit containing an imide group (-C(O)-N(R)-C(O)-), where R represents an organic group. The imide structure has high thermal stability, chemical corrosion resistance and good mechanical properties. By introducing the imide structure into the molecular chain of the alkali-soluble photocurable resin, it is beneficial to improve the comprehensive performance of the alkali-soluble photocurable resin, thereby expanding the application of the alkali-soluble photocurable resin in solder resist inks.

[0073] In addition, there is a compatibility problem in the physical blending of the traditional alkali-soluble photocurable resin and the polyimide resin. The polyimide resin added to the traditional alkali-soluble photocurable resin is insoluble in the traditional alkali-soluble photocurable resin or the added polyimide resin is prone to phase separation with the traditional alkali-soluble photocurable resin, resulting in unsatisfactory thermodynamic properties of the composite cured product. However, in the embodiments of the present application, since the imide structure is directly introduced into the molecular chain structure of the alkali-soluble photocurable resin, there are no problems such as phase separation, which can reduce the phenomenon of agglomeration that is easily caused by physical blending in the alkali-soluble photocurable resin.

[0074] In summary, the molecular chain of the alkali-soluble photocurable resin provided by the embodiments of the present application simultaneously contains a photosensitive group, an alkali-soluble group, and an imide structure. By directly introducing the imide structure into the molecular chain structure of the alkali-soluble photocurable resin, on the one hand, the thermomechanical properties of the alkali-soluble photocurable resin can be enhanced, and on the other hand, the alkali-soluble photocurable resin can form a uniform and stable resin solution in a solvent, thereby improving the comprehensive performance of the alkali-soluble photocurable resin.

[0075] In some embodiments, in formula (I), R1 is selected from organic groups containing at least one of a halogen substituent, a carbonyl group, an ether group, a phenyl group, an ester group, and an alkynyl group. Here, the carbonyl group (-C=O), the alkynyl group, etc. can also serve as photosensitive groups to further improve the photocuring performance of the alkali-soluble photocurable resin, while the ester group (-COO-) can serve as an alkali-soluble group to further improve the effect of imaging the alkali-soluble photocurable resin by alkali water development. As an example, R1 can be an organic group containing a halogen substituent, an organic group containing a carbonyl group, an organic group containing an ether group, an organic group containing a phenyl group, an organic group containing an ester group, an organic group containing an alkynyl group, an organic group containing an ether group and a phenyl group, an organic group containing an ether group and an ester group, or an organic group containing a phenyl group and an ester group.

[0076] In some embodiments, in formula (I), R1 is selected from one of the following groups:

[0077]

[0078] where represents the connection point on the organic group. When R1 is selected from the above groups, the synthesis difficulty of the alkali-soluble photocurable resin is relatively low.

[0079] In some embodiments, in formula (I) and formula (II), R2 is selected from organic groups containing at least one of a benzene ring, a siloxy group, an ether group, a nitrogen heterocycle, and a carboxyl group. As an example, R2 can be an organic group containing a benzene ring, an organic group containing a siloxy group, an organic group containing an ether group, an organic group containing a nitrogen heterocycle, an organic group containing a carboxyl group, an organic group containing an ether group and a benzene ring, an organic group containing a benzene ring and a nitrogen heterocycle, an organic group containing a benzene ring and an ester group, or an organic group containing a benzene ring, a nitrogen heterocycle, and an ester group.

[0080] In some embodiments, in formula (I) and formula (II), R2 is selected from one of the following groups:

[0081]

[0082]

[0083]

[0084] wherein represents the connection point on the organic group. When R2 is selected from the above groups, the synthesis difficulty of the alkali-soluble photocurable resin is relatively low.

[0085] In some embodiments, n is any one of 1 to 10. As an example, n is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. Generally, the larger n is, the longer the chain length of the imide structure is, which is beneficial to further increasing the molecular weight of the alkali-soluble photocurable resin and improving the thermodynamic, electrical and hydrophobic properties of the alkali-soluble photocurable resin.

[0086] In some embodiments, the number-average molecular weight of the following carbon structural unit in formula (Ⅰ) is 500 g / mol to 5000 g / mol:

[0087]

[0088] This carbon structural unit contains an imide group (-C(O)-N(R)-C(O)-), which is also called an imide structure.

[0089] As an example, the number-average molecular weight of this imide structure is 500 g / mol, 1000 g / mol, 1500 g / mol, 2000 g / mol, 2500 g / mol, 3000 g / mol, 3500 g / mol, 4000 g / mol, 4500 g / mol or 5000 g / mol. The number-average molecular weight of this imide structure should not be too large, otherwise it is easy to cause a decrease in reaction activity.

[0090] In some embodiments, the number-average molecular weight of the following carbon structural unit in formula (Ⅱ) is 500 g / mol to 5000 g / mol:

[0091]

[0092] This carbon structural unit contains an imide group (-C(O)-N(R)-C(O)-), which is also called an imide structure.

[0093] As an example, the number-average molecular weight of this imide structure is 500 g / mol, 1000 g / mol, 1500 g / mol, 2000 g / mol, 2500 g / mol, 3000 g / mol, 3500 g / mol, 4000 g / mol, 4500 g / mol or 5000 g / mol. The number-average molecular weight of this imide structure should not be too large, otherwise it is easy to cause a decrease in reaction activity.

[0094] In some embodiments, the acid value of the alkali-soluble photocurable resin is 30 mg KOH / g to 200 mg KOH / g. Generally, the acid value of the alkali-soluble photocurable resin is related to the alkali-soluble groups on the alkali-soluble photocurable resin. The size of the acid value will affect the alkali solubility of the alkali-soluble photocurable resin, and thus affect the development effect of the alkali-soluble photocurable resin. Generally, if the acid value of the alkali-soluble photocurable resin is too small, it will be difficult for the alkali-soluble photocurable resin to dissolve sufficiently, resulting in an unsmooth development process. However, if the acid value of the alkali-soluble photocurable resin is too large, it will cause overdevelopment, making it difficult to depict pattern details. As an example, the acid value of the alkali-soluble photocurable resin is 30 mg KOH / g, 40 mg KOH / g, 60 mg KOH / g, 80 mg KOH / g, 100 mg KOH / g, 120 mg KOH / g, 140 mg KOH / g, 160 mg KOH / g, 180 mg KOH / g or 200 mg KOH / g.

[0095] In some embodiments, the number average molecular weight of the alkali-soluble photocurable resin is 5000 g / mol to 20000 g / mol. The number average molecular weight of the alkali-soluble photocurable resin has an important influence on the solubility, viscosity of the alkali-soluble photocurable resin, and the mechanical properties of the dry film after curing. Generally, the lower the number average molecular weight of the alkali-soluble photocurable resin, the better the solubility. The higher the number average molecular weight of the alkali-soluble photocurable resin, the higher the viscosity, and the mechanical strength of the dry film after curing of the alkali-soluble photocurable resin is improved, and at the same time, the elastic modulus is also improved. By controlling the number average molecular weight of the alkali-soluble photocurable resin to be 5000 g / mol to 20000 g / mol, the solubility, viscosity of the alkali-soluble photocurable resin, and the mechanical properties of the dry film after curing can be effectively balanced. As an example, the number average molecular weight of the alkali-soluble photocurable resin is 5000 g / mol, 6000 g / mol, 7000 g / mol, 8000 g / mol, 9000 g / mol, 10000 g / mol, 12000 g / mol, 14000 g / mol, 16000 g / mol, 18000 g / mol or 20000 g / mol.

[0096] According to the second aspect of the embodiments of the present application, the embodiments of the present application provide a method for preparing an alkali-soluble photocurable resin, including:

[0097] S1. Performing a polycondensation reaction on an acid anhydride monomer and a diamine monomer in a first solvent to obtain a polyamic acid, wherein the acid anhydride monomer includes a carboxylic acid anhydride monomer, and the polyamic acid is a carboxylic acid-terminated polyamic acid;

[0098] S2. Performing a chemical imidization treatment on the carboxylic acid-terminated polyamic acid to obtain a carboxylic acid-terminated polyimide oligomer;

[0099] S3. Esterify the carboxyl-terminated polyimide oligomer with a polyfunctional epoxide compound to obtain a polyfunctional epoxide compound containing an imide structure;

[0100] S4. Esterify the polyfunctional epoxide compound containing an imide structure with an unsaturated carboxylic acid to obtain an esterified product;

[0101] S5. React the esterified product with a polyanhydride to obtain an alkali-soluble photocurable resin.

[0102] In step S1, the carboxylic acid anhydride monomer containing a carboxyl group refers to an organic monomer containing a carboxyl group (-COOH) and an acid anhydride group (-CO-O-CO-). The diamine monomer refers to an organic monomer containing two amino groups (-NH2). The carbonyl carbon in the carboxylic acid anhydride monomer containing a carboxyl group can react with the amino group in the diamine monomer to form an amide bond (-NH-CO-). Specifically, the carboxylic acid anhydride monomer containing a carboxyl group and the diamine monomer undergo a polycondensation reaction to form a carboxyl-terminated polyamic acid. That is, the carbonyl carbon of the acid anhydride group in the carboxylic acid anhydride monomer containing a carboxyl group reacts with the amino group in the diamine monomer to form an amide bond, and the carboxyl group in the carboxylic acid anhydride monomer containing a carboxyl group is retained. That is, the carboxylic acid anhydride monomer containing a carboxyl group also serves as a capping agent at the same time. The polyamic acid is an oligomer containing an amide group. It can be understood that the molecular chain of the carboxyl-terminated polyamic acid contains at least a carboxyl group and an amide bond.

[0103] In step S2, the chemical imidization treatment of the carboxyl-terminated polyamic acid specifically refers to converting the amide bond in the carboxyl-terminated polyamic acid into an imide bond (-C(O)-N(R)-C(O)-), so that the polyamic acid as an oligomer is converted into a polyimide oligomer, that is, the carboxyl-terminated polyamic acid is converted into a carboxyl-terminated polyimide oligomer. It can be understood that the carboxyl-terminated polyimide oligomer contains an imide structure, that is, the molecular chain of the carboxyl-terminated polyimide oligomer contains at least a carboxyl group and an imide bond.

[0104] In step S3, the polyfunctional epoxide compound refers to a class of organic compounds with multiple functional groups, which contains at least two epoxy groups. In addition to the epoxy group, the functional epoxide compound usually also includes other functional groups, including but not limited to an ether group (-O-), a ketone group (-CO-), an aldehyde group (-CHO), a carboxyl group (-COOH), a hydroxyl group (-OH), etc. Optionally, the polyfunctional epoxide compound is a polyfunctional epoxy resin.

[0105] The esterification reaction between the carboxyl-terminated polyimide oligomer and the polyfunctional epoxide is specifically that the carboxyl group on the carboxyl-terminated polyimide oligomer undergoes a ring-opening reaction with the epoxy group in the polyfunctional epoxide to form an ester group and a hydroxyl group (-OH), thereby obtaining a polyfunctional epoxide containing an imide structure. It can be understood that the molecular chain of the polyfunctional epoxide containing an imide structure contains an imide structure. Usually, only a part of the epoxy groups in the polyfunctional epoxide react with the carboxyl groups on the carboxyl-terminated polyimide oligomer in step S3, while the other part of the epoxy groups remain. That is to say, the molecular chain of the polyfunctional epoxide containing an imide structure contains at least a hydroxyl group, an imide group, and an epoxy group at the same time. In this case, the polyfunctional epoxide containing an imide structure is an epoxy group-terminated epoxide, such as an epoxy group-terminated epoxy resin.

[0106] In step S4, the molecular structural formula of the unsaturated carboxylic acid contains not only a carboxyl group (-COOH), but also at least one double bond (-C=C-) or triple bond (-C≡C-). The esterification reaction between the polyfunctional epoxide containing an imide structure and the unsaturated carboxylic acid is specifically that the carboxyl group in the unsaturated carboxylic acid undergoes a ring-opening reaction with the epoxy group on the polyfunctional epoxide containing an imide structure to form an ester group and a hydroxyl group (-OH), thereby obtaining an esterified product. It can be understood that the molecular chain of the esterified product contains at least a hydroxyl group and an imide group at the same time.

[0107] In step S5, the reaction between the esterified product and the polybasic anhydride is specifically that the anhydride group in the polybasic anhydride reacts with the hydroxyl group on the esterified product to generate an ester group.

[0108] In some embodiments, the diamine monomer includes at least one of 4,4'-diaminodiphenyl ether, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, aminopropyl-terminated polydimethylsiloxane, 3,5-diamino-1,2,4-triazole, diaminopyridine, 2-(4-aminophenyl)-5-aminobenzimidazole, 2,2'-bis[4-(4-aminophenoxyphenyl)]propane, 6,6'-diamino-3,3'-methylenedibenzoic acid, 1H-indazole-4,7-diamine, 2,2'-diamino-4,4'-bithiazole, 3,6-diaminocarbazole, methyl 2-(3,6-diamino-9H-carbazol-9-yl)acetate, 2,5-diaminobenzothiazole, 2,6-benzothiazolediamine, tert-butyl (6-amino-4-methylbenzo[d]thiazol-2-yl)carbamate, 4-methoxy-1,3-benzothiazole-2,6-diamine, melamine, 2,4-diamino-6-(2-fluorophenyl)-1,3,5-triazine, 2,4-diamino-6-(4-chlorophenyl)-1,3,5-triazine, 2,4-diamino-6-[4-(trifluoromethyl)phenyl]-1,3,5-triazine, 2,4-diamino-6-(3-fluorophenyl)-1,3,5-triazine, 2,4-diamino-6-[3-(trifluoromethyl)phenyl]-1,3,5-triazine, 2,4-diamino-6-(4-methylphenyl)-1,3,5-triazine, 2,4-diamino-6-(3,5-difluorophenyl)-1,3,5-triazine, 2,4-diamino-6-(4-bromophenyl)-1,3,5-triazine, 2,4-diamino-6-(4-methoxyphenyl)-1,3,5-triazine, 2,3-diaminophenazine, methylguanamine, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine, and 4,6-diaminopyrimidine.

[0109] In some embodiments, in step S1, the carboxylic anhydride monomer includes at least one of trimellitic anhydride and 1,3-dioxo-1,3-dihydroisobenzofuran-4-carboxylic acid.

[0110] In some embodiments, in step S1, the molar ratio of the carboxylic anhydride monomer to the diamine monomer is 2 to 2.5:1. By controlling the molar ratio of the carboxylic anhydride monomer to the diamine monomer to be 2 to 2.5:1, the two amino groups on one diamine monomer can respectively react with the anhydride groups on two carboxylic anhydride monomers. As an example, the molar ratio of the carboxylic anhydride monomer to the diamine monomer is 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, or 2.5:1.

[0111] In some embodiments, in step S1, the first solvent is a polar organic solvent. Polar organic solvents generally have high solubility, which is conducive to the full dissolution of each reaction material in the polar organic solvent and promotes the progress of chemical reactions. Optionally, the polar organic solvent includes at least one of N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), tetrahydrofuran, m-cresol, γ-butyrolactone, tetramethylurea, dimethyl sulfoxide, hexamethylphosphoric triamide, and chloroform.

[0112] In some embodiments, in step S1, when carrying out the polycondensation reaction of the carboxylic anhydride monomer and the diamine monomer, a dianhydride monomer is further added, so that the dianhydride monomer and the carboxylic anhydride monomer together carry out the polycondensation reaction with the diamine monomer. The dianhydride monomer refers to an organic monomer containing two acid anhydride groups (-CO-O-CO-). In the case of adding the dianhydride monomer, generally, the two acid anhydride groups on the dianhydride monomer react with the amino groups on different diamine monomers respectively, while the carboxylic anhydride monomer reacts with the other amino group on the diamine monomer that does not react with the acid anhydride group of the dianhydride monomer, thereby obtaining a carboxyl-terminated polyamic acid. It can be understood that on the molecular chain of the carboxyl-terminated polyamic acid, the middle part of the molecular chain is formed by the reaction of the dianhydride monomer and the diamine monomer, while the two ends of the molecular chain are formed by the reaction of the carboxylic anhydride monomer and the diamine monomer. That is to say, the addition of the dianhydride monomer can increase the chain length of the molecular chain of the carboxyl-terminated polyamic acid, that is, increase the molecular weight of the carboxyl-terminated polyamic acid, and further ultimately increase the molecular weight of the alkali-soluble photocurable resin and improve the thermodynamic properties, electrical properties and hydrophobic properties of the alkali-soluble photocurable resin.

[0113] In some embodiments, in step S1, the dianhydride monomer includes at least one of pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-diphenylethertetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3,4,4-diphenylsulfonetetracarboxylic dianhydride, 4,4'-phenylenedioxydiphthalic anhydride, hexafluorodiacid anhydride, 1,2-ethylenedi[1,3-dihydro-1,3-dioxoisobenzofuran-5-carboxylate], bisphenol A dianhydride, glycerol bis(tridecyltrimellitate) acetate, 2,3,3',4'-biphenyltetracarboxylic dianhydride, p-phenylenebis(trimellitate) dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, and 4,4'-(ethyne-1,2-diyl)diphthalic anhydride.

[0114] In some embodiments, in step S1, when performing a polycondensation reaction on a carboxylic anhydride monomer and a diamine monomer, a dianhydride monomer is further added, and the polycondensation reaction of the dianhydride monomer and the carboxylic anhydride monomer with the diamine monomer together includes:

[0115] S11. Under a first temperature and a first protective atmosphere, add the carboxylic anhydride monomer to a first solvent and dissolve the carboxylic anhydride monomer in the first solvent;

[0116] S12. Add the diamine monomer to the first solvent and stir and react for a first period of time;

[0117] S13. Add the dianhydride monomer to the first solvent and carry out a polycondensation reaction to form a carboxyl-terminated polyamic acid solution.

[0118] Optionally, during the above reaction process, the first temperature is 0°C to 60°C; the first protective atmosphere is a nitrogen atmosphere; the first period of time is 2 h to 12 h. Here, the stirring reaction means that a chemical reaction occurs under stirring conditions. As an example, the first temperature is 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C or 60°C; the first period of time is 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, 11 h or 12 h.

[0119] In some embodiments, in step S2, the number-average molecular weight of the carboxyl-terminated polyimide oligomer is 500 g / mol to 5000 g / mol. Controlling the number-average molecular weight of the carboxyl-terminated polyimide oligomer is beneficial to controlling the number-average molecular weight of the finally obtained alkali-soluble photocurable resin, so that the obtained alkali-soluble photocurable resin has better comprehensive properties. As an example, the number-average molecular weight of the carboxyl-terminated polyimide oligomer is 500 g / mol, 1000 g / mol, 1500 g / mol, 2000 g / mol, 2500 g / mol, 3000 g / mol, 3500 g / mol, 4000 g / mol, 4500 g / mol or 5000 g / mol. If the number-average molecular weight of the carboxyl-terminated polyimide oligomer is too large, the reaction activity is likely to decrease.

[0120] In some embodiments, in step S2, the chemical imidization treatment of the carboxyl-terminated polyamic acid to obtain the carboxyl-terminated polyimide oligomer includes:

[0121] Under a second temperature and a second protective atmosphere, mix a dehydrating agent and a catalyst with the carboxyl-terminated polyamic acid, stir and react for a second period of time to chemically imidize the polyamic acid into a polyimide, and perform a purification and drying treatment to obtain the carboxyl-terminated polyimide oligomer.

[0122] Optionally, during the above reaction process, the second temperature is 90°C to 150°C; the second protective atmosphere is a nitrogen atmosphere; the second duration is 24 h to 30 h. As an example, the second temperature is 90°C, 100°C, 110°C, 120°C, 130°C, 140°C or 150°C; the second duration is 24 h, 25 h, 26 h, 27 h, 28 h, 29 h or 30 h.

[0123] In some embodiments, in step S2, the dehydrating agent includes at least one of acid anhydride, acetyl chloride and thionyl chloride, and the catalyst includes tertiary amine.

[0124] In some embodiments, in step S2, the molar ratio of the dehydrating agent to the catalyst is (1 - 1.2):1, such as 1:1, 1.05:1, 1.1:1, 1.15:1, or 1.2:1. When the dehydrating agent includes acid anhydride and the catalyst includes tertiary amine, the molar ratio of the acid anhydride to the tertiary amine is (1 - 1.2):1.

[0125] In some embodiments, the acid anhydride includes at least one of acetic anhydride, trifluoroacetic anhydride and phthalic anhydride; the tertiary amine includes at least one of pyridine and triethylamine.

[0126] In some embodiments, in step S3, the polyfunctional epoxide includes at least one of difunctional epoxy resin and trifunctional epoxy resin. Difunctional epoxy resin refers to an epoxy resin containing two epoxy groups in each molecule. As an example, the difunctional epoxy resin includes bisphenol A type epoxy resin. Trifunctional epoxy resin is an epoxy resin having three reactive functional groups.

[0127] In some embodiments, in step S3, the polyfunctional epoxide includes polyfunctional epoxy resin, and the polyfunctional epoxy resin includes at least one of bisphenol A novolac type epoxy resin, naphthalene type epoxy resin, phenol novolac epoxy resin, glycidylamine type epoxy resin, o-cresol novolac epoxy resin, alkylphenol novolac type epoxy resin, dicyclopentadiene type epoxy resin, tetraphenylethane type epoxy resin, trihydroxybenzene methane type epoxy resin, diglycidyl phthalate resin, and epoxide of the condensate of phenol and aromatic aldehyde having phenolic hydroxyl group.

[0128] In some embodiments, in step S3, the carboxyl-terminated polyimide oligomer and the polyfunctional epoxide are subjected to an esterification reaction to obtain a polyfunctional epoxide containing an imide structure, including:

[0129] At a third temperature and in a third protective atmosphere, dissolve the carboxyl-terminated polyimide oligomer in a first solvent, and add a polyfunctional epoxy compound to cause an esterification reaction between the carboxyl-terminated polyimide oligomer and the polyfunctional epoxy compound to obtain a polyfunctional epoxy compound containing an imide structure.

[0130] Optionally, during the above reaction process, the third temperature is 90°C to 150°C; the third protective atmosphere is a nitrogen atmosphere. As an example, the third temperature is 90°C, 100°C, 110°C, 120°C, 130°C, 140°C or 150°C.

[0131] In some embodiments, in step S4, the unsaturated carboxylic acid includes at least one of an unsaturated monocarboxylic acid and an unsaturated polycarboxylic acid. The unsaturated monocarboxylic acid has only one carboxyl group; while the unsaturated polycarboxylic acid has two or more carboxyl groups.

[0132] In some embodiments, in step S4, the unsaturated carboxylic acid includes at least one of acrylic acid, methacrylic acid, acrylic acid dimer, cinnamic acid, β-styrylacrylic acid, β-furylacrylic acid, α-cinnamic acid, crotonic acid, the reaction product of a saturated or unsaturated dianhydride and a hydroxy-containing (meth)acrylate, and the reaction product of a saturated or unsaturated dibasic acid and an unsaturated monoglycidyl compound.

[0133] In some embodiments, in step S5, the polyanhydride includes at least one of a saturated polyanhydride and an unsaturated polyanhydride.

[0134] In some embodiments, in step S5, the polyanhydride includes at least one of a dianhydride, a polyaromatic carboxylic anhydride, and an acid anhydride derivative. Optionally, the dianhydride includes at least one of maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride. Optionally, the polyaromatic carboxylic anhydride includes at least one of trimellitic anhydride, pyromellitic dianhydride, and benzophenone tetracarboxylic dianhydride. Optionally, the acid anhydride derivative includes 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexenyl-1,2-dicarboxylic anhydride.

[0135] In some embodiments, in step S5, the polyanhydride includes at least one of tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and succinic anhydride. Thus, it is beneficial to reduce the viscosity of the alkali-soluble photocurable resin, improve the chemical stability, thermal stability, and adhesion of the alkali-soluble photocurable resin, and promote the crosslinking effect.

[0136] In some embodiments, in step S5, the temperature for reacting the esterified product with the polyanhydride is 70°C to 120°C, such as 70°C, 80°C, 90°C, 100°C, 110°C, or 120°C.

[0137] In some embodiments, the method for preparing the alkali-soluble photocurable resin provided in the second aspect of the embodiments of the present application is used to prepare the alkali-soluble photocurable resin provided in the first aspect of the embodiments of the present application.

[0138] According to the third aspect of the embodiments of the present application, the embodiments of the present application provide a photocurable resin composition. By mass, the photocurable resin composition includes 100 parts of an alkali-soluble photocurable resin, 15 parts to 45 parts of a thermosetting resin, and 0.5 parts to 2 parts of a photoinitiator; the alkali-soluble photocurable resin is the alkali-soluble photocurable resin as described above or the alkali-soluble photocurable resin prepared by the method for preparing the alkali-soluble photocurable resin as described above.

[0139] As an example, the mass of the thermosetting resin in the photocurable resin composition is 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, or 45 parts.

[0140] As an example, the mass of the photoinitiator in the photocurable resin composition is 0.5 parts, 0.7 parts, 0.9 parts, 1.1 parts, 1.3 parts, 1.5 parts, 1.8 parts, or 2.0 parts.

[0141] In some embodiments, by mass, the photocurable resin composition further includes 5 parts to 15 parts of a photopolymerizable monomer. Adding a photopolymerizable monomer to the photocurable resin composition is beneficial to improving the crosslinking degree during the curing of the photocurable resin composition. As an example, the mass of the photopolymerizable monomer in the photocurable resin composition is 5 parts, 7 parts, 9 parts, 11 parts, 13 parts, or 15 parts.

[0142] In some embodiments, the photopolymerizable monomer includes at least one of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, methyl (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, lauryl (meth)acrylate, dipropylene glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, neopentyl glycol diethoxy / propyloxy di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0143] In some embodiments, the photopolymerizable monomer includes dipentaerythritol hexa(meth)acrylate. The molecular structure of dipentaerythritol hexa(meth)acrylate contains multiple acrylate functional groups, which can provide a high degree of crosslinking, enhancing the mechanical strength and heat resistance of the final material. Compared with other high-crosslinking monomers, dipentaerythritol hexaacrylate has better flexibility and is suitable for applications that require a certain degree of elasticity.

[0144] In some embodiments, the thermosetting resin includes at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, dimethylxylenol epoxy resin, biphenol epoxy resin, alicyclic epoxy resin, hydrogenated bisphenol A epoxy resin, brominated bisphenol A epoxy resin, phenolic epoxy resin, triphenolmethane epoxy resin, N-glycidyl epoxy resin, isocyanuric acid triglycidyl ester, cresol-soluble epoxy resin, 2,6-dimethylphenol dimer diglycidyl ether, alicyclic epoxy resin, and xylene epoxy resin.

[0145] In some embodiments, the thermosetting resin includes bisphenol A epoxy resin. After curing, bisphenol A epoxy resin provides high strength and rigidity, can form strong adhesion with a variety of substrates, and is beneficial to enhancing the scope of application and mechanical properties of the photocurable resin composition.

[0146] In some embodiments, the photoinitiator includes at least one of photoinitiator 907, oxime ester-based photoinitiators, acylphosphine oxide-based photoinitiators, acetophenone-based photoinitiators, benzoin and its alkyl ether photoinitiators, anthraquinone-based photoinitiators, thioxanthone-based photoinitiators, ketal-based photoinitiators, and benzophenone-based photoinitiators. Optionally, the oxime ester-based photoinitiator includes at least one of OXE-1 and OXE-2. Optionally, the acylphosphine oxide-based photoinitiator includes 2,4,6-trimethylbenzoyl diphenylphosphine oxide. Optionally, the acetophenone-based photoinitiator includes at least one of acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 2,2-diethoxy-2-phenylacetophenone. Optionally, the benzoin and its alkyl ether photoinitiators include at least one of benzoin, benzoin ethyl ether, benzoin methyl ether, and benzoin isopropyl ether. Optionally, the anthraquinone-based photoinitiator includes at least one of 2-methylanthraquinone, 2-tert-butylanthraquinone, 2-ethylanthraquinone, and 1-chloroanthraquinone. Optionally, the thioxanthone-based photoinitiator includes at least one of 2,4-dimethylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone. Optionally, the ketal-based photoinitiator includes at least one of acetophenone dimethyl ketal and benzyl dimethyl ketal. Optionally, the benzophenone-based photoinitiator includes benzophenone and 4,4'-bis(diethylamino)benzophenone.

[0147] In some embodiments, the photoinitiator includes an oxime ester photoinitiator, which has a high initiation efficiency under ultraviolet light irradiation, can rapidly initiate the polymerization reaction, complete the curing process in a short time, and improve the curing efficiency.

[0148] In some embodiments, by mass, the photocurable resin composition further includes 10 to 80 parts of an inorganic filler. Adding an inorganic filler to the photocurable resin composition is beneficial to improving the mechanical properties of the cured photocurable resin composition. As an example, the mass of the inorganic filler in the photocurable resin composition is 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, or 80 parts.

[0149] In some embodiments, the inorganic filler includes at least one of barium sulfate, silica, calcium oxide, barium titanate, magnesium carbonate, calcium carbonate, talc powder, alumina, aluminum hydroxide, titanium oxide, fumed silica, clay, mica powder, and kaolin. Barium sulfate and alumina can improve the strength and rigidity of the material after curing the photocurable resin composition and enhance wear resistance. Aluminum hydroxide and alumina have high thermal stability and are suitable for high-temperature applications. Silica and calcium carbonate can improve the fluidity of the photocurable resin composition, making the photocurable resin composition easy to process.

[0150] In some embodiments, the average particle size of the inorganic filler is 0.001 μm - 20 μm. Reducing the average particle size of the inorganic filler helps to improve the dispersibility of the inorganic filler in the photocurable resin composition, is beneficial to reducing the risk of precipitation and aggregation of the inorganic filler in the photocurable resin composition, and further improves the stability of the performance of the photocurable resin composition. As an example, the average particle size of the inorganic filler is 0.001 μm, 0.01 μm, 0.1 μm, 1 μm, 2 μm, 4 μm, 6 μm, 8 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, or 20 μm.

[0151] In some embodiments, the average particle size of the inorganic filler is 0.05 μm - 15 μm. As an example, the average particle size of the inorganic filler is 0.05 μm, 0.1 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, or 15 μm.

[0152] In some embodiments, the average particle size of the inorganic filler is 0.05 μm - 3 μm. As an example, the average particle size of the inorganic filler is 0.05 μm, 0.1 μm, 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, or 3 μm.

[0153] In some embodiments, by mass parts, the photocurable resin composition further comprises 2 to 10 parts of a curing agent. The curing agent can be used to promote the curing of the photocurable resin composition. As an example, the mass parts of the curing agent in the photocurable resin composition are 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts.

[0154] In some embodiments, the curing agent includes at least one of dicyandiamide, melamine, diethylenetriamine, triethanolamine, polyamide, vinylamine, urethane, methyloxiraneamine, and ethylenediamine.

[0155] In some embodiments, by mass parts, the photocurable resin composition further comprises a pigment. Optionally, the pigment includes at least one of phthalocyanine green, phthalocyanine blue, titanium dioxide, carbon black, and lithopone. Optionally, the pigment is a pigment free of free halogens, which is beneficial to reducing the environmental pollution by halogens.

[0156] In some embodiments, the photocurable resin composition further comprises 0.05 to 20 parts of an additive. As an example, the mass parts of the additive in the photocurable resin composition are 0.05 parts, 1 part, 2 parts, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts or 20 parts.

[0157] In some embodiments, the additive includes at least one of a curing accelerator, a photoinitiator assistant, a diluent, a thixotropic thickener, a leveling agent, a polymerization inhibitor, a tackifier, an antifoaming agent, a coupling agent, an antioxidant, and a rust inhibitor.

[0158] In some embodiments, the photocurable resin composition further comprises a second solvent. When the photocurable resin composition further comprises a second solvent, the photocurable resin composition is a photocurable resin composition glue solution.

[0159] In some embodiments, the second solvent includes at least one of a ketone solvent, an aromatic solvent, an alcohol ether solvent, a glycol ether acetate solvent, an ester solvent, an alcohol solvent, an aliphatic hydrocarbon solvent, and a petroleum solvent. Optionally, the alcohol ether solvent includes at least one of cellulose, methylcellulose, butylcellulose, carbitol, methyl carbitol, butyl carbitol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monobutyl ether, and dipropylene glycol monobutyl ether. Optionally, the ester solvent includes at least one of ethyl acetate, butyl acetate, carbitol acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol butyl ether acetate. Optionally, the alcohol solvent includes at least one of ethanol, propanol, ethylene glycol, and propylene glycol. Optionally, the aliphatic hydrocarbon solvent includes at least one of octane and decane. Optionally, the petroleum solvent includes at least one of petroleum ether, naphtha, and hydrogenated naphtha. Optionally, the ketone solvent includes at least one of methyl ethyl ketone, cyclohexanone, butanone, and isophorone. Optionally, the aromatic solvent includes at least one of toluene, xylene, and pseudocumene.

[0160] In some embodiments, the solid content of the photocurable resin composition is 40 wt% to 85 wt%. Here, the solid content of the photocurable resin composition refers to the mass ratio of other components in the photocurable resin composition except the second solvent. As an example, the solid content of the photocurable resin composition is 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, or 85 wt%.

[0161] In some embodiments, the photocurable resin composition further includes a second solvent, and the preparation method of the photocurable resin composition includes:

[0162] Providing a mixed glue solution, the mixed glue solution containing an alkali-soluble photocurable resin and a second solvent;

[0163] Adding a thermosetting resin and a photoinitiator to the mixed glue solution to obtain a photocurable resin composition.

[0164] According to the fourth aspect of the embodiments of the present application, the embodiments of the present application provide a photosensitive dry film, and the photosensitive dry film includes a cured product of the photocurable resin composition as described above.

[0165] In some embodiments, the method for preparing a photosensitive dry film includes: spreading a photocurable resin composition solution on a clean wafer substrate (i.e., silicon wafer) by coating, and soft-baking the coated wafer substrate on a hot plate at 70°C to 80°C for 20 min to 30 min to remove part of the organic solvents, obtaining a coating film with a film thickness of 20 μm to 30 μm. Exposing the coating film under an ultraviolet exposure machine to obtain a dry film. Finally, performing thermal curing in a nitrogen atmosphere, and curing the exposed dry film at 170°C for 1 hour to obtain a cured product.

[0166] In some embodiments, the method for preparing a photosensitive dry film includes: spreading a photocurable resin composition solution on a PET film by doctor blade coating, and soft-baking the coated PET film on a hot plate at 70°C to 80°C for 20 min to 30 min to remove part of the organic solvents, obtaining a doctor blade coating film with a film thickness of 20 μm to 30 μm. Thermally pressing the doctor blade coating film on the surface of the wafer substrate to obtain a film on the wafer surface, and then, taking the film on the wafer surface as a reference, performing an exposure process on the mask pattern. Developing the exposed film on the wafer surface to form a patterned film. Finally, performing thermal curing in a nitrogen atmosphere, and curing the exposed and developed patterned film at 170°C for 1 hour to obtain a cured product.

[0167] According to the fifth aspect of the embodiments of the present application, the embodiments of the present application provide a semiconductor device including the photosensitive dry film as described above.

[0168] The following is an illustration with specific embodiments.

[0169] Example 1

[0170] This example provides a photocurable resin composition.

[0171] The preparation process of the photocurable resin composition includes:

[0172] S1. Preparing a carboxyl-terminated polyimide oligomer:

[0173] Under a nitrogen atmosphere at room temperature, 52.3609 g of 2,2'-bis[4-(4-aminophenoxyphenyl)]propane was added to 670 g of N-methylpyrrolidone. After 2,2'-bis[4-(4-aminophenoxyphenyl)]propane was completely dissolved, 48.2246 g of trimellitic anhydride was then added, and the mixture was mechanically stirred for about 6 hours to carry out a polycondensation reaction to form a carboxyl-terminated polyamic acid solution. Subsequently, under a nitrogen atmosphere at about 90 °C, 35.3295 g of acetic anhydride and 38.8667 g of triethylamine were slowly added dropwise and rapidly stirred for 24 hours to chemically imidize the polyamic acid into polyimide, obtaining a polyimide solution. The above polyimide solution was slowly added dropwise to anhydrous ethanol, and a mechanical stirring paddle was equipped to continuously stir. After the addition was completed, a white polyimide precipitate was collected by suction filtration using a Buchner funnel, placed in a vacuum oven and dried for 48 h to constant weight to obtain a carboxyl-terminated polyimide oligomer.

[0174] S2. Preparation of alkali-soluble photocurable resin:

[0175] Under a nitrogen atmosphere at 110 °C, using 0.6080 g of pyrocatechol as an inhibitor and 0.6626 g of triphenylphosphine as a catalyst, 84.9960 g of the carboxyl-terminated polyimide oligomer was dissolved in 700 g of N-methylpyrrolidone, and 120.1447 g of 2,2-bis-(4-glycidyloxybenzene)propane was added to carry out an esterification reaction and mechanically stirred for 12 hours. Subsequently, 21.8363 g of acrylic acid was added for an esterification reaction; the temperature was lowered to about 90 °C, and the obtained esterified product was reacted with 93.1531 g of tetrahydrophthalic anhydride to obtain an alkali-soluble photocurable resin. After the reaction was completed, the product was cooled to room temperature, an ethanol aqueous solution with a certain proportion was prepared, the reaction solution was slowly poured into the ethanol aqueous solution and stirred at high speed using a top-mounted stirrer. After the product precipitated, the rotation speed was reduced. After stirring for about 30 min, the product was taken out. The product was dissolved in an acetone solution using an ultrasonic instrument. After complete dissolution, these two steps were repeated about three times. Finally, the product was placed in a 45 °C constant temperature vacuum drying oven for about 48 h to remove water vapor and volatile solvents. Finally, an alkali-soluble photocurable resin was obtained. The nuclear magnetic spectrum of the alkali-soluble photocurable resin is as Figure 1 shown, and the infrared spectrum is as Figure 2 shown.

[0176] S3. Preparation of photocurable resin composition:

[0177] Dissolve 100 g of the prepared alkali-soluble photocurable resin in 54 g of carbitol acetate, and obtain a uniformly dispersed glue solution through mechanical stirring for 8 hours; then mix it with 30 g of thermosetting resin YX400, 0.6 g of melamine, 2.4 g of dicyandiamide, 1 g of photoinitiator OXE02, 7.5 g of polydiethylene glycol pentaacrylate, 37.5 g of silicon dioxide, 12.5 g of barium sulfate, 2 g of phthalocyanine green, and 50 g of diethylene glycol methyl ether acetate solvent, and stir at a speed of 1000 rpm for 6 h under mechanical stirring. After mixing evenly, grind it with a three-roll mill to finally prepare a photocurable resin composition, specifically a photocurable resin composition glue solution with a solid content of about 50 wt%.

[0178] Example 2

[0179] The difference between this example and Example 1 is that 52.3609 g of 2,2'-bis[4-(4-aminophenoxyphenyl)]propane in step S1 is replaced with 25.03 g of 4,4'-diaminodiphenyl ether, and finally a photocurable resin composition is prepared.

[0180] Example 3

[0181] The difference between this example and Example 1 is that trimellitic anhydride in step S1 is replaced with 1,3-dioxy-1,3-dihydroisobenzofuran-4-carboxylic acid, and finally a photocurable resin composition is prepared.

[0182] Example 4

[0183] The difference between this example and Example 1 is that N-methylpyrrolidone in step S1 is replaced with N,N-dimethylformamide, and finally a photocurable resin composition is prepared.

[0184] Example 5

[0185] The difference between this example and Example 1 is that 2,2-bis-(4-glycidyloxybenzene)propane in step S2 is replaced with bisphenol F epoxy resin EXA-7376, and finally a photocurable resin composition is prepared.

[0186] Example 6

[0187] The difference between this example and Example 1 is that 21.8363 acrylic acid in step S2 is replaced with 25.8090 g of crotonic acid, and finally a photocurable resin composition is prepared.

[0188] Example 7

[0189] The difference between this example and Example 1 is that 93.1531 g of tetrahydrophthalic anhydride in step S2 is replaced with 92.4960 g of hexahydrophthalic anhydride, and finally a photocurable resin composition is prepared.

[0190] Example 8

[0191] The difference between this example and Example 1 is that in step S3, carbitol acetate is replaced with diethylene glycol butyl ether acetate, and finally a photocurable resin composition is prepared.

[0192] Example 9

[0193] The difference between this example and Example 1 is that in step S2, 2,2-bis-(4-glycidyloxyphenyl)propane is replaced with o-cresol novolac epoxy resin SQCN704M, and finally a photocurable resin composition is prepared.

[0194] Example 10

[0195] The difference between this example and Example 1 is that in step S2, 93.1531 g of tetrahydrophthalic anhydride is replaced with 69.8647 g of tetrahydrophthalic anhydride, and finally a photocurable resin composition is prepared.

[0196] Example 11

[0197] The difference between this example and Example 1 is that in step S2, 93.1531 g of tetrahydrophthalic anhydride is replaced with 46.5766 g of tetrahydrophthalic anhydride, and finally a photocurable resin composition is prepared.

[0198] Example 12

[0199] The difference between this example and Example 1 is that in step S1, 32.8592 g of bisphenol A diether dianhydride is further added during the polycondensation reaction, and finally a photocurable resin composition is prepared.

[0200] Example 13

[0201] The difference between this example and Example 1 is that in step S1, 13.7702 g of pyromellitic dianhydride is further added during the polycondensation reaction, and finally a photocurable resin composition is prepared.

[0202] Example 14

[0203] The difference between this example and Example 1 is that in step S1, 19.5839 g of 4,4'-oxybisphthalic anhydride is further added during the polycondensation reaction, and finally a photocurable resin composition is prepared.

[0204] Example 15

[0205] The difference between this example and Example 1 is that in step S1, 28.0454 g of hexafluorodiacid anhydride is further added during the polycondensation reaction, and finally a photocurable resin composition is prepared.

[0206] Example 16

[0207] The difference between this example and Example 1 is that in step S1, 28.9349 g of p-phenylene-bis(trimellitic anhydride) dianhydride was continuously added during the polycondensation reaction, and finally a photocurable resin composition was prepared.

[0208] Example 17

[0209] The difference between this example and Example 1 is that in step S1, 20.3428 g of 3,3',4,4'-benzophenone tetracarboxylic dianhydride was continuously added during the polycondensation reaction, and finally a photocurable resin composition was prepared.

[0210] Comparative Example 1

[0211] The difference between this comparative example and Example 1 is that the polyimide oligomer in step S1 was not synthesized, and the carboxyl-terminated polyimide oligomer was not added during the preparation of the alkali-soluble photocurable resin in step S2.

[0212] I. Testing the photocurable resin compositions provided in each example and comparative example:

[0213] 1. Preparation of photosensitive dry film:

[0214] The photocurable resin composition solution was spread on PET by doctor blading. The doctor-bladed PET was soft-baked on a hot plate at 75 °C for 25 minutes to remove part of the organic solvent, obtaining a doctor-blade film with a thickness of 20 - 30 μm. The doctor-blade film was hot-pressed onto the surface of the wafer substrate to obtain a film on the wafer surface. Subsequently, based on the film on the wafer surface, a mask pattern was subjected to an exposure process. The exposed film on the wafer surface was developed to form a pattern film. Finally, thermal curing was carried out in a nitrogen atmosphere, and the exposed pattern film was cured at 170 °C for 1 hour to obtain a cured product.

[0215] 2. Mechanical property testing:

[0216] The dry film was cut into rectangular specimens with a length of 15 mm and a width of 3 mm. The mechanical properties of the prepared dry film were characterized by a Dynamic Thermomechanical Analyzer (DMA). When testing, the gauge length was set to 10 mm. The specimens were clamped in the DMA fixture, the average thickness value of the specimens was input, the tensile rate was set to 1 N / min, the test temperature was room temperature, and the stress-strain data of the specimens from the start of stretching to fracture were recorded in Table 1.

[0217] Table 1

[0218]

[0219] The main difference between Examples 1 to 17 and Comparative Example 1 is that an imide structure is introduced into the molecular chain structure of the alkali-soluble photocurable resin in Examples 1 to 17, and it is found that the mechanical properties of the photocurable resin composition containing the alkali-soluble photocurable resin are significantly improved after curing. This is because the introduction of the imide structure can not only enhance the thermomechanical properties of the alkali-soluble photocurable resin, but also enable the alkali-soluble photocurable resin to form a uniform and stable resin glue in the solvent, and ultimately improve the mechanical properties of the photocurable resin composition containing the alkali-soluble photocurable resin after curing.

[0220] The difference between Example 1 and Example 2 is that the diamine monomers involved in the reaction are different, the difference between Example 1 and Example 3 is that the carboxyl anhydride monomers involved in the reaction are different, the difference between Example 1 and Example 4 is that the first solvent is different, the difference between Example 1 and Examples 5 and 9 is that the multifunctional epoxy compounds are different, the difference between Example 1 and Example 6 is that the unsaturated carboxylic acids are different, and the difference between Example 1 and Example 7 is that the polyacid anhydrides are different. It is found that the mechanical properties of the photocurable resin composition after curing will be different. This is because the above factors affect the structure or molecular weight of the generated alkali-soluble photocurable resin to a certain extent, thereby making the performance of the alkali-soluble photocurable resin different. Finally, the photocurable resin composition containing the alkali-soluble photocurable resin has different mechanical properties after curing.

[0221] The difference between Example 1 and Example 8 is that the second solvent is different. It is found that the mechanical properties of the photocurable resin composition after curing will be different. This is because different second solvents have different compatibilities with alkali-soluble photocurable resins, which makes the dispersibility of alkali-soluble photocurable resins in the resin glue different, and ultimately affects the mechanical properties of the photocurable resin composition after curing.

[0222] The difference between Example 1 and Examples 10 and 11 is that the dosage of the polyacid anhydride is different. As the dosage of the polyacid anhydride decreases, the mechanical properties of the photocurable resin composition after curing deteriorate, indicating that an appropriately excessive dosage of the polyacid anhydride can improve the performance of the alkali-soluble photocurable resin, thereby improving the mechanical properties of the photocurable resin composition after curing.

[0223] The difference between Example 12-17 and Example 1-11 is that the dianhydride monomer is added simultaneously during the polycondensation reaction of the carboxyl-containing acid anhydride monomer and the diamine monomer, and it is found that the mechanical properties of the photocurable resin composition obtained in Example 12-17 are significantly improved after curing. This is because the addition of the dianhydride monomer can increase the chain length of the molecular chain of the carboxyl-terminated polyamic acid, thereby ultimately increasing the molecular weight of the alkali-soluble photocurable resin and improving the performance of the alkali-soluble photocurable resin, which is ultimately manifested as the mechanical properties of the photocurable resin composition after curing are improved.

[0224] In the description of the present application, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, features defined with "first" and "second" may explicitly or implicitly include one or more features. In the description of the present application, "a plurality of" means two or more, unless otherwise specifically defined.

[0225] In the above embodiments, the descriptions of the respective embodiments have their own emphases. For parts not detailed in a certain embodiment, reference may be made to the relevant descriptions of other embodiments.

[0226] The embodiments, implementation manners and related technical features of the present application can be combined and replaced with each other without conflict.

[0227] The above are only the preferred embodiments of the present application and do not impose any form of limitation on the present application. However, any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present application without departing from the content of the technical solution of the present application still fall within the scope of the technical solution of the present application.

Claims

1. An alkali-soluble photocurable resin, characterized in that: The structural formula of the alkali-soluble photocurable resin is shown in formula (I) or formula (II): In formula (I), R1 is selected from the following: a single bond, an oxygen atom, a sulfonyl group, and an organic group having 1 to 30 carbon atoms; In formula (I) and formula (II), n is a natural number greater than or equal to 0; R2 is selected from an organic group having 1 to 50 carbon atoms; R3 is selected from an aromatic organic group or an aliphatic organic group; R4 is selected from an organic group containing an unsaturated carbon-carbon double bond; R5 is selected from an organic group containing a carboxyl group.

2. The alkali-soluble photocurable resin according to claim 1, characterized in that: In formula (I), R1 is selected from an organic group containing at least one of a halogen substituent, a carbonyl group, an ether group, a phenyl group, an ester group and an alkynyl group.

3. The alkali-soluble photocurable resin according to claim 2, characterized in that: In formula (I), R1 is selected from one of the following groups: in Indicates the point of attachment on the organic group.

4. The alkali-soluble photocurable resin according to claim 1, characterized in that: In formula (I) and formula (II), R2 is selected from an organic group containing at least one of a benzene ring, a silyl group, an ether group, a nitrogen heterocycle and a carboxyl group.

5. The alkali-soluble photocurable resin according to claim 4, characterized in that: In formula (I) and formula (II), R2 is selected from one of the following groups: in Indicates the point of attachment on the organic group.

6. The alkali-soluble photocurable resin according to claim 1, characterized in that: n is greater than or equal to 1 and less than or equal to 10; or, The number average molecular weight of the following carbon structural units in formula (I) is 500 g / mol to 5000 g / mol: or The number average molecular weight of the following carbon structural units in formula (II) is 500 g / mol to 5000 g / mol: or, The acid value of the alkali-soluble photocurable resin is 30 mg KOH / g to 200 mg KOH / g; or The number average molecular weight of the alkali-soluble photocurable resin is 5000 g / mol to 20000 g / mol.

7. A method for preparing an alkali-soluble photocurable resin, characterized in that: include: Carrying out polycondensation reaction of anhydride monomers and diamine monomers in a first solvent to obtain polyamic acid, wherein the anhydride monomers include carboxyl-containing anhydride monomers, and the polyamic acid is carboxyl-terminated polyamic acid; Performing chemical imidization treatment on the carboxyl-terminated polyamic acid to obtain a carboxyl-terminated polyimide oligomer; The carboxyl-terminated polyimide oligomer is subjected to an esterification reaction with a multifunctional epoxy compound to obtain a multifunctional epoxy compound containing an imide structure; Esterifying the polyfunctional epoxy compound containing an imide structure with an unsaturated carboxylic acid to obtain an esterified product; The esterified product is reacted with a polyacid anhydride to obtain an alkali-soluble photocurable resin.

8. The method for preparing an alkali-soluble photocurable resin according to claim 7, characterized in that: The diamine monomers include: 4,4'-diaminodiphenyl ether, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, aminopropyl dicapped polydimethylsiloxane, 3,5-diamino-1,2,4-triazole, diaminopyridine, 2-(4-aminophenyl)-5-aminobenzimidazole, 2,2'-bis[4-(4-aminophenoxyphenyl)]propane, 6,6'-bisamino-3,3'-methylenedibenzoic acid, 1-hydrogen- Indazole-4,7-diamine, 2,2'-diamino-4,4'-bithiazole, 3,6-diaminocarbazole, 2-(3,6-diamino-9H-carbazole-9-yl)acetic acid methyl ester, 2,5-diaminobenzothiazole, 2,6-benzothiazole diamine, (6-amino-4-methylbenzo [D] thiazol-2-yl) carbamic acid tert-butyl ester, 4-methoxy-1,3-benzothiazole-2,6-diamine, benzoguanamine, 2,4-diamino-6-(2- 2,4-diamino-6-(4-chlorophenyl)-1,3,5-triazine, 2,4-diamino-6-[4-(trifluoromethyl)phenyl]-1,3,5-triazine, 2,4-diamino-6-(3-fluorophenyl)-1,3,5-triazine, 2,4-diamino-6-[3-(trifluoromethyl)phenyl]-1,3,5-triazine, 2,4-diamino-6-(4-methylphenyl)-1,3,5-triazine , at least one of 2,4-diamino-6-(3,5-difluorophenyl)-1,3,5-triazine, 2,4-diamino-6-(4-bromophenyl)-1,3,5-triazine, 2,4-diamino-6-(4-methoxyphenyl)-1,3,5-triazine, 2,3-diaminophenolazine, methylguanamine, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-thiazine, and 4,6-diaminopyrimidine; or, The carboxyl group-containing acid anhydride monomer includes at least one of trimellitic anhydride and 1,3-dioxy-1,3-dihydroisobenzofuran-4-carboxylic acid; or, The molar ratio of the carboxyl-containing anhydride monomer to the diamine monomer is 2 to 2.5:1; or, The multifunctional epoxy compound includes a multifunctional epoxy resin, and the multifunctional epoxy resin includes at least one of bisphenol A novolac epoxy resin, naphthalene epoxy resin, phenol novolac epoxy resin, glycidylamine epoxy resin, o-cresol novolac epoxy resin, alkylphenol novolac epoxy resin, dicyclopentadiene epoxy resin, tetraphenol ethane epoxy resin, trihydroxyphenylmethane epoxy resin, diglycidyl phthalate resin, and epoxy compounds of condensates of phenols and aromatic aldehydes having phenolic hydroxyl groups; or, The unsaturated carboxylic acid includes at least one of an unsaturated monocarboxylic acid and an unsaturated polycarboxylic acid; or, The polybasic acid anhydride includes at least one of a dibasic acid anhydride, a polybasic aromatic carboxylic acid anhydride and an acid anhydride derivative.

9. The method for preparing an alkali-soluble photocurable resin according to claim 7 or 8, characterized in that: When the carboxyl-containing acid anhydride monomer and the diamine monomer are subjected to polycondensation reaction, the dianhydride monomer is also added, so that the dianhydride monomer and the carboxyl-containing acid anhydride monomer are subjected to polycondensation reaction with the diamine monomer together.

10. The method for preparing an alkali-soluble photocurable resin according to claim 9, characterized in that: The dianhydride monomers include: pyromellitic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3,4,4-diphenyl sulfone tetracarboxylic dianhydride, 4,4'-diphenylene dioxydiphthalic anhydride, hexafluoroisopropylidene diphthalic anhydride, At least one of fluorine dianhydride, 1,2-ethylenebis[1,3-dihydro-1,3-dioxoisobenzofuran-5-carboxylate], bisphenol A dianhydride, glycerol bis(anhydrotrimellitate) acetate, 2,3,3',4'-biphenyltetracarboxylic dianhydride, p-phenylene-bis(trimellitate) dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, and 4,4'-(ethynyl-1,2-diyl) diphthalic anhydride.

11. A photocurable resin composition, characterized in that: The photocurable resin composition comprises, by mass, 100 parts of an alkali-soluble photocurable resin, 15 to 45 parts of a thermosetting resin, and 0.5 to 2 parts of a photopolymerization initiator; the alkali-soluble photocurable resin is an alkali-soluble photocurable resin as described in any one of claims 1 to 6 or an alkali-soluble photocurable resin prepared by the preparation method of an alkali-soluble photocurable resin as described in any one of claims 7 to 10.

12. The photocurable resin composition according to claim 11, characterized in that The photocurable resin composition further comprises 5 to 15 parts of photopolymerizable monomers by mass; or The photocurable resin composition further comprises 10 to 80 parts by mass of an inorganic filler; or The photocurable resin composition further comprises 2 to 10 parts of a curing agent by weight.

13. The photocurable resin composition according to claim 11 or 12, characterized in that: The photocurable resin composition further includes a second solvent.

14. A photosensitive dry film, characterized in that: The photosensitive dry film comprises a cured product of the photocurable resin composition according to any one of claims 11 to 13.

15. A semiconductor device, characterized in that: Comprising the photosensitive dry film as claimed in claim 14.

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