Polyimide precursor composition, method for preparing the same, and photosensitive resin composition comprising the same

Abstract

The present invention provides a polyimide precursor composition, a method for preparing the same, and a photosensitive resin composition comprising the polyimide precursor composition, the polyimide precursor composition comprising: a polyimide precursor comprising a dianhydride monomer, a diamine monomer, and an alcohol compound having an unsaturated double bond as polymerization units; and an acid having at least one carboxyl group in the molecule.

Description

[Technical Field]

[0001] This invention relates to a polyimide precursor composition, a method for preparing the same, and a method for preparing a photosensitive resin composition comprising the polyimide precursor composition. Specifically, this invention relates to a polyimide precursor composition with improved storage stability due to its ease of storage, a method for preparing the same, and a photosensitive resin composition comprising the polyimide precursor composition. [Previous Technology]

[0002] Generally speaking, polyimide (PI) is a polymer material based on amide rings. It possesses excellent chemical stability and a rigid aromatic backbone, exhibiting the highest heat resistance, chemical resistance, electrical insulation, and weather resistance among organic materials. It can be manufactured into various forms such as thin films, fibers, and membranes. Due to these properties, polyimide is used in semiconductors and electronic components as an interlayer dielectric, protective film, and sealing material.

[0003] Among them, compared with non-photosensitive polyimide, photosensitive polyimide resin is advantageous for shortening the process due to its ease of pattern formation, and has the characteristics of design freedom in terms of composition formation and size.

[0004] Conventional photosensitive polyimide precursor compositions exhibit poor storage stability when present alone in solution, often leading to problems such as clumping or precipitation. Therefore, there is a need to develop polyimide precursor compositions with improved storage stability and methods for their preparation. [Summary of the Invention]

[0005] The purpose of this invention is to provide a polyimide precursor composition with excellent storage stability by suppressing the ring-closing rate and a method for preparing the same.

[0006] Another object of the present invention is to provide a photosensitive resin composition comprising a polyimide precursor composition having excellent storage stability.

[0007] Various modifications and embodiments can be made in this invention, and specific embodiments are shown and described in detail in the drawings. However, it should be understood that this is not intended to limit the invention to the specific embodiments, but rather to include all modifications, equivalents, and substitutions contained within the spirit and scope of the invention.

[0008] The terminology used in this application is for describing specific embodiments only and is not intended to limit the invention. Unless the context clearly indicates otherwise, singular expressions should include plural expressions. In this specification, terms such as "comprise" or "have" are intended to indicate the presence of features, quantities, steps, operations, elements, components or combinations thereof described in the specification, and should not be construed as excluding the possibility of the presence or addition of one or more other features, quantities, steps, operations, elements, components or combinations thereof.

[0009] When quantities, concentrations or other values ​​or parameters in this document are given as a range, preferred range or a list of upper and lower expected values, it should be understood that all ranges formed by any pair of any upper or preferred value with any lower or preferred value are specifically disclosed, regardless of whether the range is disclosed individually.

[0010] Unless otherwise stated, when a range of values ​​is stated herein, it is intended that the endpoints of that range and the scope of the invention within that range are not limited to the specific values ​​stated when the range is defined.

[0011] As used herein, "dianhydride" is intended to include its precursors or derivatives, also known as "dianhydride acid," "dianhydride," or "acid dianhydride." These products may not technically be dianhydrides, but will still react with diamines to form polyamides, and polyamides can be converted back to polyimides.

[0012] As used herein, "diamine" is intended to include its precursors or derivatives, which may not technically be diamines but still react with dianhydrides to form polyamides, and polyamides can be converted back to polyimides.

[0013] Unless otherwise defined, all terms used herein, including technical or scientific terms, shall have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Terms such as those defined in common dictionaries shall be interpreted as having a meaning consistent with their meaning in the relevant technical context and shall not be interpreted in an idealized or overly formal sense unless expressly defined in this application. Specific details of embodiments of the invention will now be described.

[0014] This invention relates to a polyimide precursor composition, a photosensitive resin composition comprising the polyimide precursor, and a method for preparing the polyimide precursor composition.

[0015] Polyimide precursor composition:

[0016] The present invention provides a polyimide precursor composition comprising: a polyimide precursor comprising an aromatic dianhydride monomer, a diamine monomer and an alcohol compound having an unsaturated double bond as polymerization units; and an acid having at least one carboxyl group in the molecule.

[0017] Specifically, the polyimide precursor composition can suppress the ring-closing rate of the polyimide precursor composition by including an acid having at least one carboxyl group in the molecule to provide excellent storage stability.

[0018] The polyimide precursor composition may be a negative polyimide precursor composition.

[0019] An acid having at least one carboxyl group in its molecule may include at least one selected from mandelic acid, oxalic acid, glycolic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, succinic acid, acetic acid, malic acid, citric acid and malonic acid, and preferably at least one selected from mandelic acid, oxalic acid, succinic acid, citric acid, acetic acid and malic acid, more preferably at least one selected from mandelic acid, oxalic acid, succinic acid and acetic acid, and even more preferably at least one selected from mandelic acid, oxalic acid and succinic acid, which has the effect of providing better storage stability.

[0020] Generally, in the preparation of polyimide precursor compositions, the presence of a basic catalyst (such as pyridine) promotes the amide reaction even at room temperature. Therefore, it is necessary to lower the pH of the polyimide precursor composition to inhibit the amide reaction. Acids with at least one carboxyl group in their molecule have different acid dissociation constants (pKa). The lower the pKa, the stronger the acid. The more acids with lower pKa in the polyimide precursor composition, the more the amide reaction (ring closure) is inhibited, resulting in better storage stability.

[0021] The dianhydride monomer may include at least one selected from the following substances: biphenyl dianhydride (BPDA), oxydiphthalic dianhydride (ODPA), pyromellitic dianhydride (PMDA), 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), dibenzo-3,3',4,4'-tetracarboxylic dianhydride (DSDA), bis(3,4-dicarboxyphenyl)thionyl dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2,2-bis( 3,4-Dicarboxyphenyl)propane dianhydride, p-phenylenebis(trimethoxymethyl phthalate monoester anhydride), p-biphenylbis(trimethoxymethyl phthalate monoester anhydride), m-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, p-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)phenyl dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)phenyl dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2-bis[(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA), 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and 4,4'-(2,2-hexafluoroisopropylidene)diphthalic dianhydride.

[0022] Preferably, the dianhydride monomer may include biphenyl dianhydride (BPDA) and oxydiphthalic dianhydride (ODPA).

[0023] The amount of biphenyl dianhydride (BPDA) in the total dianhydride monomer can be greater than 0 mol% and less than or equal to 50 mol%. For example, its upper limit can be 50 mol%, 45 mol%, 40 mol%, 37 mol%, 35 mol%, 34 mol%, 33 mol%, 32 mol%, 31 mol%, or 30 mol% or lower, and its lower limit can be 1 mol%, 2 mol%, 3 mol%, 4 mol%, 5 mol%, 6 mol%, 7 mol%, 8 mol%, 9 mol%, or 10 mol% or higher.

[0024] The amount of oxydiphthalic dianhydride (ODPA) in the total dianhydride monomer can be 50 mol% or more and less than 100 mol%. For example, its upper limit can be 99 mol%, 98 mol%, 97 mol%, 96 mol%, 95 mol%, 94 mol%, 93 mol%, 92 mol%, 91 mol% or 90 mol% or less, and its lower limit can be 50 mol%, 55 mol%, 60 mol%, 63 mol%, 65 mol%, 66 mol%, 67 mol%, 68 mol%, 69 mol% or 70 mol% or more.

[0025] The diamine monomer may include at least one selected from the following substances: 4,4'-diaminodiphenyl ether (4,4'-ODA), 1,4-diaminobenzene (PPD), 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB), 2,2'-dimethyl-4,4'-diaminobiphenyl (meta-toluidine), 2,2-diaminophenoxyphenylpropane (BAPP), m-phenylenediamine, 3,3'-dimethylbenzidine, 2,2'-dimethylbenzidine, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminobenzoic acid (DABA), 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane 3,3'-Dicarboxy-4,4'-Diaminodiphenylmethane, 3,3',5,5'-Tetramethyl-4,4'-Diaminodiphenylmethane, 4,4'-Diaminobenzophenone, 3,3'-Dimethoxybenzidine, 2,2'-Dimethoxybenzidine, 3,3'-Diaminodiphenyl ether, 3,3'-Diaminodiphenyl sulfide, 3,4'-Diaminodiphenyl sulfide, 4,4'-Diaminodiphenyl sulfide, 3,3'-Diaminodiphenyl ketone, 3,4'-Diaminodiphenyl ketone, 4,4'-Diaminodiphenyl ketone, 3,3'-Diamino-4,4'-Dichlorobenzophenone, 3,3'-Diamino-4,4'-Dimethoxybenzophenone 3,3'-Diaminodiphenylmethane, 3,4'-Diaminodiphenylmethane, 4,4'-Diaminodiphenylmethane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 3,3'-Diaminodiphenylene, 3,4'-Diaminodiphenylene, 4,4'-Diaminodiphenylene, 1,3-bis(3-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(3-aminophenyl)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenoxy) Benzene (TPE-R), 1,4-bis(3-aminophenoxy)benzene (TPE-Q), 1,3-bis(3-aminophenoxy)-4-trifluoromethylbenzene, 3,3'-diamino-4-(4-phenyl)phenoxybenzophenone, 3,3'-diamino-4,4'-bis(4-phenylphenoxy)benzophenone, 1,3-bis(3-aminophenyl sulfide)benzene, 1,3-bis(4-aminophenyl sulfide)benzene, 1,4-bis(4-aminophenyl sulfide)benzene, 1,3-bis(3-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis[2-(4-aminophenyl)isopropyl]benzene, 1,4-bis[2-(3-aminophenyl)isopropyl]benzene, 1,4-Bis[2-(4-aminophenyl)isopropyl]benzene, 3,3'-bis(3-aminophenoxy)biphenyl, 3,3'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[3-(3-aminophenoxy)phenyl]ether, bis[3-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether, bis[3-(3-aminophenoxy)phenyl]ether [3-(4-aminophenoxy)phenyl] ketone, bis[4-(3-aminophenoxy)phenyl] ketone, bis[4-(4-aminophenoxy)phenyl] ketone, bis[3-(3-aminophenoxy)phenyl] sulfide, bis[3-(4-aminophenoxy)phenyl] sulfide, bis[4-(3-aminophenoxy)phenyl] sulfide, bis[4-(4-aminophenoxy)phenyl] sulfide, bis[3-(3-aminophenoxy)phenyl] sulfide, bis[3-(4 ... [4-(3-aminophenoxy)phenyl] ion, bis[4-(4-aminophenoxy)phenyl] ion, bis[3-(3-aminophenoxy)phenyl]methane, bis[3-(4-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy)phenyl]methane, 2,2-bis[3-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane The mixture comprises propane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3-hexafluoropropane, 2,2-bis[3-(4-aminophenoxy)phenyl]-1,1,1,3,3-hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3-hexafluoropropane, and preferably includes 4,4'-diaminodiphenyl ether (4,4'-ODA).

[0026] An alcohol compound having an unsaturated double bond may include at least one selected from 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), 2-hydroxypropyl methacrylate and 2-hydroxypropyl acrylate, and preferably may include 2-hydroxyethyl methacrylate (HEMA).

[0027] The polyimide precursor composition may further comprise a solvent. The solvent may be an aprotic polar organic solvent, and specifically may include at least one selected from the following: N,N'-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N,N'-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), diethylacetamide (DEAc), N-ethyl-2-pyrrolidone (NEP), N,N'-diethylformamide (DEF), dimethylpropionamide (DMPA), and γ-butyrolactone (GBL).

[0028] The polyimide precursor composition may further comprise a dehydrating condensing agent. The dehydrating condensing agent may include at least one selected from the group consisting of, for example, dicyclohexylcarbodiimide (DCC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), N,N'-diisopropylcarbodiimide (DIC), 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate.

[0029] Polyimide precursors may include polyamide esters and polyamides.

[0030] The weight-average molecular weight of the polyimide precursor composition can be from 1,000 g / mol to 100,000 g / mol. The lower limit of the weight-average molecular weight can be 1,500 g / mol, 2,000 g / mol, 2,500 g / mol, or 3,000 g / mol or higher, and the upper limit of the weight-average molecular weight can be 90,000 g / mol, 80,000 g / mol, 70,000 g / mol, 60,000 g / mol, 50,000 g / mol, 40,000 g / mol, 35,000 g / mol, or 32,000 g / mol or lower. The weight-average molecular weight can be measured by gel permeation chromatography (GPC) analysis using N-methyl-2-pyrrolidone (NMP) as a solvent.

[0031] Method for preparing polyimide precursor compositions:

[0032] The present invention provides a method for preparing a polyimide precursor composition, comprising: (a) polymerizing a dianhydride monomer, a diamine monomer and an alcohol compound having an unsaturated double bond to prepare a polyimide precursor; and (b) mixing the polyimide precursor with an acid having at least one carboxyl group in the molecule to prepare a polyimide precursor composition.

[0033] Polyimide precursors may include polyamide esters and polyamides.

[0034] Specifically, conventional polyimide precursor compositions undergo amide imidization (ring closure) via catalysts (such as pyridine) used in the preparation of polyimide precursors. Therefore, there is a problem that they are difficult to use as negative polyimide precursors over time after preparation. The present invention can prepare polyimide precursor compositions with excellent storage stability by using an acid having at least one carboxyl group in the molecule to inhibit the ring closure rate of the polymer.

[0035] For every 1 mole equivalent of polyimide precursor, the amount of acid having at least one carboxyl group in the molecule can be from 0.5 mole equivalents to 1.5 mole equivalents. For example, the upper limit can be 1.5 mole equivalents, 1.4 mole equivalents, 1.3 mole equivalents, 1.2 mole equivalents and 1.1 mole equivalents or lower, and the lower limit can be 0.5 mole equivalents, 0.6 mole equivalents, 0.7 mole equivalents, 0.75 mole equivalents, 0.8 mole equivalents, 0.85 mole equivalents, 0.9 mole equivalents, 0.95 mole equivalents or higher. It is undesirable when the amount of acid with at least one carboxyl group in the molecule is less than 0.5 molar equivalents, because the storage stability of the prepared polyimide precursor composition deteriorates. It is also undesirable when the amount of acid with at least one carboxyl group in the molecule exceeds 1.5 molar equivalents, because the properties of the polyimide precursor composition deteriorate due to hydrolysis, or the storage stability efficiency is not improved, which is inefficient.

[0036] Step (a) may be a step (a-1) of mixing dianhydride monomers and alcohol compounds having unsaturated double bonds to prepare reactants, and then polymerizing the reactants and diamine monomers to prepare polyimide precursors.

[0037] Step (a) may be step (a-2) of polymerizing dianhydride monomers and diamine monomers to prepare polyamide, and then reacting polyamide with an alcohol compound having unsaturated double bonds to prepare a polyimide precursor.

[0038] For every 1 mol equivalent of dianhydride monomer, the amount of alcohol compound having unsaturated double bonds can be from 2 to 3 mol equivalents. For example, the upper limit can be 2.8 mol equivalents, 2.7 mol equivalents, 2.6 mol equivalents, 2.55 mol equivalents, 2.5 mol equivalents, 2.45 mol equivalents, 2.4 mol equivalents, 2.35 mol equivalents, 2.3 mol equivalents or lower, and the lower limit can be 2.03 mol equivalents, 2.05 mol equivalents, 2.07 mol equivalents, 2.08 mol equivalents, 2.09 mol equivalents, 2.1 mol equivalents or higher. When the amount of alcohol compound having unsaturated double bonds is less than 2 mol equivalents, it is likely that a polyimide precursor composition with excellent negative properties cannot be obtained. It is also undesirable to use an alcohol compound with unsaturated double bonds in amounts exceeding 3 molar equivalents, because the amount of polyimide precursor composition prepared may not increase relative to the amount of alcohol compound used, which is economically inefficient.

[0039] In the method for preparing the polyimide precursor composition, after mixing the polyimide precursor with an acid having at least one carboxyl group in the molecule, step (b) may further include purification, filtration and drying.

[0040] Acids having at least one carboxyl group in the molecule may not be removed from polyimide precursors by purification, filtration and drying.

[0041] In addition, purification may include purification methods conventionally used in polymer synthesis, including reprecipitation, such as alcohol precipitation.

[0042] Photosensitive resin composition:

[0043] This invention provides a photosensitive resin composition comprising a polyimide precursor composition. The photosensitive resin composition according to this invention can be a negative photosensitive resin composition.

[0044] Specifically, the photosensitive resin composition may contain additives commonly used in the field of photosensitive resin composition technology, such as photoinitiators, crosslinking agents, surfactants, etc.

[0045] Beneficial effects:

[0046] The polyimide precursor composition according to the present invention can suppress the ring-closing rate and provide excellent storage stability by including an acid having at least one carboxyl group in the molecule.

Implementation Method

[0048] The following exemplary embodiments are provided to aid in understanding the present invention. These embodiments are provided merely to facilitate a better understanding of the invention, but the scope of the invention is not limited to these embodiments.

[0049] <Example 1: Preparation of polyimide precursor composition>

[0050] Example 1-1

[0051] In a reactor, 30 mol% biphenyl dianhydride (BPDA), 70 mol% oxydiphthalic dianhydride (ODPA), 210 mol% 2-hydroxyethyl methacrylate (HEMA) and 100 mol% pyridine were stirred in γ-butyrolactone (GBL) solvent at room temperature for 10 hours or longer to synthesize a BPDA-ODPA-HEMA solution.

[0052] After adding 202 mol% dicyclohexylcarbodiimide (DCC) at -10°C, the BPDA-ODPA-HEMA solution was stirred for 30 minutes. Then, 98 mol% 4,4'-diaminodiphenyl ether (4,4'-ODA) was added, the temperature was raised to room temperature, and the resulting mixture was stirred for 2 hours to prepare the polyimide precursor.

[0053] 100 mol% mandelic acid was added to the polyimide precursor prepared above, and the mixture was stirred for 1 hour. The mixture was then filtered to separate the product, and then precipitated in 2 to 4 times its weight of ethanol to remove unreacted substances. The obtained precipitate was redissolved in γ-butyrolactone (GBL), and the redissolved solution was precipitated in 8 to 10 times its weight of ultrapure water and dried to obtain the final polyimide precursor composition.

[0054] Examples 1-2 to Examples 1-6

[0055] Each polyimide precursor composition was prepared in the same manner as in Examples 1-1, except that different types of acids having at least one carboxyl group in the molecule were used, as shown in Table 1 below.

[0056] Comparative Example 1-1

[0057] The polyimide precursor composition was prepared in the same manner as in Example 1-1, except that mandelic acid was not used, which is different from Example 1-1 which used mandelic acid.

[0058] Table 1 below shows the types and amounts of monomers used to prepare the polyimide precursor compositions according to Examples 1-1 to 1-6 and Comparative Example 1-1, respectively. Table 1 Classification Dihydride monomer diamine monomer alcohols with unsaturated double bonds Acids with at least one carboxyl group in their molecule Example 1-1 BPDA (30 mol%) ODPA (70 mol%) ODA (98 mol%) HEMA (210 mol%) Mandelic acid (100 mol%) Examples 1-2 BPDA (30 mol%) ODPA (70 mol%) ODA (98 mol%) HEMA (210 mol%) Oxalic acid (100 mol%) Examples 1-3 BPDA (30 mol%) ODPA (70 mol%) ODA (98 mol%) HEMA (210 mol%) Succinic acid (100 mol%) Examples 1-4 BPDA (30 mol%) ODPA (70 mol%) ODA (98 mol%) HEMA (210 mol%) Citric acid (100 mol%) Examples 1-5 BPDA (30 mol%) ODPA (70 mol%) ODA (98 mol%) HEMA (210 mol%) Acetic acid (100 mol%) Examples 1-6 BPDA (30 mol%) ODPA (70 mol%) ODA (98 mol%) HEMA (210 mol%) Malic acid (100 mol%) Comparative Example 1-1 BPDA (30 mol%) ODPA (70 mol%) ODA (98 mol%) HEMA (210 mol%) -

[0059] <Example 2: Preparation of photosensitive resin composition>

[0060] Example 2-1

[0061] The polyimide precursor composition prepared according to Example 1-1 and the photoinitiator were mixed in an organic solvent and filtered through a filter to prepare a negative photosensitive resin composition.

[0062] Examples 2-2 to 2-6

[0063] Each photosensitive resin composition was prepared in the same manner as in Examples 2-1, except that the polyimide precursor compositions prepared in Examples 1-2 to 1-6 were used instead of the polyimide precursor compositions prepared in Example 1-1.

[0064] <Experimental Examples: Characterization of Polyimide Precursor Compositions>

[0065] Experimental Example 1: Measurement of weight-average molecular weight (Mw)

[0066] Using N-methyl-2-pyrrolidone (NMP) as a solvent, the polyimide precursor compositions prepared according to Examples 1-1 to 1-6 and Comparative Example 1-1 were analyzed by gel permeation chromatography (GPC) to measure the weight-average molecular weight. The results are shown in Table 2 below.

[0067] Experimental Example 2: Measurement of Loop Closure Rate

[0068] The ring-closure rate of each polyimide precursor composition prepared according to Examples 1-1 to 1-6 and Comparative Example 1-1 was measured by H-NMR.

[0069] Figure 1 shows the H-NMR measurement results of the polyimide precursor composition prepared according to Example 1-1, Figure 2 shows the H-NMR measurement results of the polyimide precursor composition prepared according to Example 1-2, and Figure 3 shows the H-NMR measurement results of the polyimide precursor composition prepared according to Comparative Example 1-1.

[0070] The H-NMR measurements of the polyimide precursor composition (Figures 1 to 3) confirmed that when 7 ppm was set to 1 among the peaks of 7 to 7.1 ppm on the x-axis, the integral value of 7.1 ppm gradually increased with the increase of the ring-closure rate. This is because the benzene peak of the ODA portion in the molecular structure shifted when the ring-closure reaction proceeded, which suggests that ring closure occurred during the reaction.

[0071] The ring-closure ratio was calculated using the H-NMR measurement results and Equation 1 below. More specifically, the ring-closure ratio after polymerization and drying (ring-closure ratio A) and the ring-closure ratio after the storage stability test of Experimental Example 3 below (ring-closure ratio B) were measured twice in total, and the results are shown in Table 2 below.

[0072] [Equation 1]

[01] Loop closure rate (%) = IB / (IA+IB) x 100

[02] In Equation 1,

[03] IA is the 7.0 ppm integral value of the H-NMR measurement result, and IB is the 7.1 ppm integral value of the H-NMR measurement result.

[0073] Experimental Example 3: Confirmation of Storage Stability

[0074] The polyimide precursor compositions prepared according to Examples 1-1 to 1-6 and Comparative Example 1-1 were each dissolved in 35% γ-butyrolactone (GBL) and placed in an oven at 60°C for 5 days. The results are shown in Table 2 according to the following criteria.

[0075] A indicates that the closed-loop rate increased by less than 10%.

[0076] B indicates that the closed-loop rate increases by 10% or more but is less than 20%.

[0077] C indicates that the loop closure rate increases by 20% or more.

[0078] D: Unmeasurable

[0079] Experimental Example 4: Measurement of Haze

[0080] After the storage stability test was conducted according to the above experimental example 3, the turbidity of the solution was measured using a haze meter, and the results are shown in Table 2 below.

[0081] Table 2 below summarizes the molecular weight, ring closure rate, storage stability, and haze measurement results of the polyimide precursor compositions prepared according to Examples 1-1 to 1-6 and Comparative Example 1-1. Table 2 Classification Example 1-1 Examples 1-2 Examples 1-3 Examples 1-4 Examples 1-5 Examples 1-6 Comparative Example 1-1 Molecular weight (Mw) (g / mol) 29,000 31,000 34,200 29,500 30,300 32,800 28,700 Loop closure rate A (%) 17.35 14.52 18.69 21.25 27.53 20.63 20.63 Closed-loop rate B (%) 25.06 26.07 20.63 48.71 34.64 46.80 - Storage stability A B A C B C D Haze (%) 0.27 0.31 0.21 82.93 79.17 93.59 immeasurable

[0082] Table 2 shows that Examples 1-1 to Examples 1-6, which contain acids having at least one carboxyl group in the molecule (e.g., mandelic acid, oxalic acid, succinic acid, citric acid, acetic acid, and malic acid), have higher storage stability than Comparative Example 1-1, which does not contain acids having at least one carboxyl group in the molecule.

[0083] In addition, it can be confirmed that the polyimide precursor compositions of Examples 1-1 to 1-6 maintained a low ring-closure rate.

[0084] Meanwhile, Table 2 shows that the polyimide precursor composition of Comparative Example 1-1 has a storage stability of D (not measurable). The measurement of the ring-closure rate requires a step of dissolving in DMSO-d6 solvent in an NMR apparatus. However, during the storage stability test, as the amide reaction (ring closure) proceeded, the polyimide precursor composition of Comparative Example 1-1 did not dissolve in DMSO4-d6 solvent, and therefore could not be measured by NMR. Therefore, the ring-closure rate B could not be measured, nor could the storage stability (D).

[0085] Meanwhile, Table 2 shows that the haze of the polyimide precursor compositions of Examples 1-1 to 1-6 can be measured, but the haze of the polyimide precursor composition of Comparative Example 1-1 cannot be measured. This is because the polyimide precursor composition of Comparative Example 1-1 forms a gel as the amide reaction (ring closure) proceeds. This confirms that the polyimide precursor compositions according to the present invention have excellent storage stability.

[0086] In this specification, detailed descriptions of contents that can be fully understood and inferred by those skilled in the art have been omitted, and many variations and modifications can be made without changing the technical spirit or basic configuration of the invention, in addition to the specific exemplary embodiments described herein. Therefore, the invention can also be practiced in ways different from those specifically described and shown herein and understood by those skilled in the art. [Simplified Explanation of the Diagram]

[0047] Figure 1 shows the 1H-NMR measurement results of the polyimide precursor compositions prepared according to Examples 1-1. Figure 2 shows the 1H-NMR measurement results of the polyimide precursor compositions prepared according to Examples 1-2. Figure 3 shows the 1H-NMR measurement results of the polyimide precursor compositions prepared according to Comparative Examples 1-1.

Claims

1. A polyimide precursor composition comprising: a polyimide precursor, said polyimide precursor comprising a dianhydride monomer, a diamine monomer, and an alcohol compound having an unsaturated double bond as polymerization units; and an acid having at least one carboxyl group in the molecule; wherein, The acid having at least one carboxyl group in the molecule includes at least one selected from the following: mandelic acid, oxalic acid, glycolic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, succinic acid, acetic acid, malic acid, citric acid, and malonic acid.

2. The polyimide precursor composition as claimed in claim 1, wherein the polyimide precursor composition is a negative polyimide precursor composition.

3. The polyimide precursor composition as claimed in claim 1, wherein the dianhydride monomer comprises at least one selected from the group consisting of: biphenyl dianhydride (BPDA), oxydiphthalic dianhydride (ODPA), pyromellitic dianhydride (PMDA), 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), dibenzo-3,4,3',4'-tetracarboxylic dianhydride (DSDA), bis(3,4-dicarboxyphenyl)thiodianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, and bis(3,4-dicarboxyphenyl)methane. Dimethyl phthalate, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, p-phenylenebis(trimethoxymethyl phthalate monoester anhydride), p-biphenylbis(trimethoxymethyl phthalate monoester anhydride), m-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, p-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)phenyl dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)phenyl dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2-bis[(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA), 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and 4,4'-(2,2-hexafluoroisopropylidene)diphthalic dianhydride.

4. The polyimide precursor composition as claimed in claim 3, wherein the dianhydride monomer comprises biphenyl dianhydride (BPDA) and oxydiphthalic dianhydride (ODPA).

5. The polyimide precursor composition as claimed in claim 3, wherein the amount of biphenyl dianhydride (BPDA) in the total dianhydride monomer is greater than 0 mol% and less than or equal to 50 mol%.

6. The polyimide precursor composition as claimed in claim 3, wherein the amount of oxydiphthalic dianhydride (ODPA) in the total dianhydride monomer is 50 mol% or greater than 50 mol% and less than 100 mol%.

7. The polyimide precursor composition as claimed in claim 1, wherein the diamine monomer comprises at least one selected from the group consisting of: 4,4'-diaminodiphenyl ether (4,4'-ODA), 1,4-diaminobenzene (PPD), 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB), 2,2'-dimethyl-4,4'-diaminobiphenyl (meta-toluidine), 2,2-diaminophenoxyphenylpropane (BAPP), m-phenylenediamine, 3,3'-dimethylbenzidine, 2,2'-dimethylbenzidine, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminobenzoic acid (DABA), 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3' -Dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminobenzonitrile, 3,3'-dimethoxybenzidine, 2,2'-dimethoxybenzidine, 3,3'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 3,3'-diamino-4,4'-dichlorobenzophenone, 3, 3'-Diamino-4,4'-Dimethoxybenzophenone, 3,3'-Diaminodiphenylmethane, 3,4'-Diaminodiphenylmethane, 4,4'-Diaminodiphenylmethane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 3,3'-Diaminodiphenylene, 3,4'-Diaminodiphenylene, 4,4'-Diaminodiphenylene, 1,3-bis(3-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(3-aminophenyl)benzene, 1,4-bis(4- (Aminophenyl)benzene, 1,3-bis(4-aminophenoxy)benzene (TPE-R), 1,4-bis(3-aminophenoxy)benzene (TPE-Q), 1,3-bis(3-aminophenoxy)-4-trifluoromethylbenzene, 3,3'-diamino-4-(4-phenyl)phenoxybenzophenone, 3,3'-diamino-4,4'-di(4-phenylphenoxy)benzophenone, 1,3-bis(3-aminophenyl sulfide)benzene, 1,3-bis(4-aminophenyl sulfide)benzene, 1,4-bis(4-aminophenyl sulfide)benzene, 1,3-bis(3-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis[2-(4-aminophenyl)isopropyl]benzene, 1,4-Bis[2-(3-aminophenyl)isopropyl]benzene, 1,4-bis[2-(4-aminophenyl)isopropyl]benzene, 3,3'-bis(3-aminophenoxy)biphenyl, 3,3'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[3-(3-aminophenoxy)phenyl]ether, bis[3-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether [-aminophenoxy)phenyl] ether, bis[3-(3-aminophenoxy)phenyl] ketone, bis[3-(4-aminophenoxy)phenyl] ketone, bis[4-(3-aminophenoxy)phenyl] ketone, bis[4-(4-aminophenoxy)phenyl] ketone, bis[3-(3-aminophenoxy)phenyl] sulfide, bis[3-(4-aminophenoxy)phenyl] sulfide, bis[4-(3-aminophenoxy)phenyl] sulfide, bis[4-(4-aminophenoxy)phenyl] sulfide, bis[3-(3 ... [3-(4-aminophenoxy)phenyl] benzo[3-(4-aminophenoxy)phenyl] benzo[3-(4-aminophenoxy)phenyl] benzo[3-(4-aminophenoxy)phenyl] benzo[3-(4-aminophenoxy)phenyl] benzo[3-(4-aminophenoxy)phenyl] methane, bis[3-(4-aminophenoxy)phenyl] methane, bis[4-(3-aminophenoxy)phenyl] methane, bis[4-(4-aminophenoxy)phenyl] methane, 2,2-bis[3-(3-aminophenoxy)phenyl] propane, 2,2-bis[3-(4-aminophenoxy)phenyl] propane [3-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3-hexafluoropropane, 2,2-bis[3-(4-aminophenoxy)phenyl]-1,1,1,3,3-hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3-hexafluoropropane and 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3-hexafluoropropane.

8. The polyimide precursor composition as claimed in claim 1, wherein the alcohol compound having unsaturated double bonds comprises at least one selected from the group consisting of 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), 2-hydroxypropyl methacrylate, and 2-hydroxypropyl acrylate.

9. A photosensitive resin composition comprising the polyimide precursor composition as described in claim 1.

10. A method for preparing a polyimide precursor composition, comprising: (a) Polymerizing dianhydride monomers, diamine monomers, and alcohol compounds having unsaturated double bonds to prepare polyimide precursors; (b) mixing the polyimide precursor with an acid having at least one carboxyl group in the molecule to prepare the polyimide precursor composition; wherein the acid having at least one carboxyl group in the molecule includes at least one selected from the group consisting of mandelic acid, oxalic acid, glycolic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, succinic acid, acetic acid, malic acid, citric acid, and malonic acid.

11. The method of claim 10, wherein the amount of an acid having at least one carboxyl group in the molecule is 0.5 to 1.5 molar equivalents relative to each 1 molar equivalent of the polyimide precursor.

12. The method of claim 10, wherein step (a) is step (a-1) of mixing the dianhydride monomer and the alcohol compound having unsaturated double bonds to prepare a reactant, and then polymerizing the reactant and the diamine monomer to prepare the polyimide precursor.

13. The method of claim 10, wherein step (a) is step (a-2) of polymerizing the dianhydride monomer and the diamine monomer to prepare polyamide, and then reacting the polyamide with the alcohol compound having unsaturated double bonds to prepare the polyimide precursor.

14. The method of claim 10, wherein the amount of the alcohol compound having unsaturated double bonds is 2 to 3 mol equivalents relative to each 1 mol equivalent of the dianhydride monomer.

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