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

Abstract

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

Description

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

[0001] The present invention relates to a polyimide precursor composition, a method for preparing the same, and a method for preparing a photosensitive resin composition comprising the same. More specifically, the present invention relates to a polyimide precursor composition that is easy to store and thus has improved storage stability, a method for preparing the same, and a photosensitive resin composition comprising the same.

[0002] Polyimide (PI) is a polymer material that possesses the highest levels of heat resistance, chemical resistance, electrical insulation, chemical resistance, and weather resistance among organic materials, based on a rigid aromatic backbone and an imide ring with excellent chemical stability. It can be manufactured into various forms such as films, fibers, and membranes. Due to these properties, polyimide is used as an interlayer insulating film, protective film, and sealing material in semiconductors and electronic components.

[0003] Among them, photosensitive polyimide resin is advantageous in shortening the process because it is easier to form a pattern than non-photosensitive polyimide, and has the characteristic of freedom in design in terms of composition formation and size.

[0004] Existing photosensitive polyimide precursor compositions, when present alone in solution, have poor storage stability, leading to agglomeration and precipitation. Therefore, research is needed into polyimide precursor compositions that are easy to store and methods for producing them.

[0005] The purpose of the present invention is to provide a polyimide precursor composition having excellent storage stability by suppressing the rate of conversion and a method for producing the same.

[0006] In addition, the purpose is to provide a photosensitive resin composition including a polyimide precursor composition having excellent storage stability.

[0007] The present invention is susceptible to various modifications and embodiments. Therefore, specific embodiments are illustrated and described in detail. However, this is not intended to limit the present invention to specific embodiments, but rather to encompass all modifications, equivalents, and alternatives falling within the spirit and technical scope of the present invention.

[0008] The terminology used in this application is only used to describe specific embodiments and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this application, it should be understood that the terms "comprise" or "have" indicate the presence of a feature, number, step, operation, component, part, or combination thereof described in the specification, but do not exclude in advance the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.

[0009] When amounts, concentrations, or other values ​​or parameters are given herein as a range, preferred range, or enumeration of an upper preferred value and a lower preferred value, it should be understood that this specifically discloses any range formed by any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed.

[0010] When a range of numerical values ​​is mentioned in this specification, unless otherwise stated, it is intended that the endpoints of the range and the scope of the invention within the range are not limited to the specific values ​​mentioned in defining the range.

[0011] As used herein, "dianhydride" is intended to include precursors or derivatives thereof, also referred to as "dianhydric acids," "dianhydrides," or "acid dianhydrides." While these may not technically be dianhydrides, they will nonetheless react with diamines to form polyamic acids, which can then be converted to polyimides.

[0012] As used herein, "diamine" is intended to include precursors or derivatives thereof, which may not technically be diamines, but which will nonetheless react with a dianhydride acid to form a polyamic acid, which in turn can be converted to a polyimide.

[0013] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Terms defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the relevant technology, and shall not be construed in an idealized or overly formal sense unless explicitly defined herein. Specific details for implementing the invention are described below.

[0014] The present invention relates to a polyimide precursor composition, a photosensitive resin composition comprising the same, and a method for producing 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 has an excellent storage stability effect by suppressing the conversion rate of the polyimide precursor composition by including an acid having one or more carboxyl groups in the molecule.

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

[0019] The acid having at least one carboxyl group in the molecule may include 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, preferably at least one selected from the group consisting of mandelic acid, oxalic acid, succinic acid, citric acid, acetic acid, and malic acid, more preferably at least one selected from the group consisting of mandelic acid, oxalic acid, succinic acid, and acetic acid, and even more preferably at least one selected from the group consisting of mandelic acid, oxalic acid, and succinic acid, and in this case, the storage stability is more excellent.

[0020] In general, when manufacturing a polyimide precursor composition, if a basic catalyst (such as pyridine) is present, the imidization reaction is promoted even at room temperature, so the pH of the polyimide precursor composition must be lowered to suppress this. Acids having one or more carboxyl groups in the molecule have different acid dissociation constants (pKa). The lower the pKa, the greater the strength of the acid. The lower the pKa in the polyimide precursor composition, the more the imidization reaction (ring closure) is suppressed, resulting in excellent storage stability.

[0021] The above dianhydride monomers are biphenyl tetracarboxylic dianhydride (BPDA), oxydiphthalic dianhydride (ODPA), pyromellitic dianhydride (PMDA), 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), diphenylsulfone-3,4,3',4'-tetracarboxylic dianhydride (DSDA), bis(3,4-dicarboxyphenyl)sulfide dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2,2-Bis(3,4-dicarboxyphenyl)propane dianhydride, p-phenylenebis(trimellitic monoester acid anhydride), p-biphenylenebis(trimellitic monoester acid anhydride), m-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, p-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2-bis〔(3,4-dicarboxy phenoxy)phenyl〕propane dianhydride (BPADA), 2,3,6,7-naphthalene tetracarboxylic acid It may include at least one selected from the group consisting of dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and 4,4'-(2,2-hexafluoroisopropylidene)diphthalic acid dianhydride.

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

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

[0024] The content of the oxydiphthalic dianhydride (ODPA) among the total dianhydride monomers may be 50 mol% or more and less than 100 mol%. For example, the upper limit may 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 the lower limit may 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 above diamine monomers are 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 (m-tolidine), 2,2-bisaminophenoxyphenylpropane (BAPP), metaphenylenediamine, 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'-diaminobenzanilide, 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 sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 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'-Diaminodiphenylsulfoxide, 3,4'-Diaminodiphenylsulfoxide, 4,4'-Diaminodiphenylsulfoxide, 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-aminophenylsulfide)benzene, 1,3-bis(4-aminophenylsulfide)benzene, 1,4-bis(4-aminophenylsulfide)benzene, 1,3-bis(3-aminophenylsulfone)benzene, 1,3-bis(4-aminophenylsulfone)benzene, 1,4-bis(4-aminophenylsulfone)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〕ketone, bis〔3-(4-aminophenoxy)phenyl〕ketone, bis〔4-(3-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〕sulfone, bis〔3-(4-aminophenoxy)phenyl〕sulfone, bis〔4-(3-aminophenoxy)phenyl〕sulfone, bis〔4-(4-aminophenoxy)phenyl〕sulfone, bis〔3-(3-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, 2,2-bis〔4-(3-aminophenoxy)phenyl〕propane, 2,2-bis〔3-(3-aminophenoxy)phenyl〕-1,1,1,3,3,3-hexafluoropropane, 2,2-bis〔3-(4-aminophenoxy)phenyl〕-1,1,1,3,3,3-hexafluoropropane, 2,It may include at least one selected from the group consisting of 2-bis〔4-(3-aminophenoxy)phenyl〕-1,1,1,3,3,3-hexafluoropropane and 2,2-bis〔4-(4-aminophenoxy)phenyl〕-1,1,1,3,3,3-hexafluoropropane, and preferably 4,4'-diaminodiphenyl ether (4,4'-ODA).

[0026] The alcohol compound having the above unsaturated double bond may include at least one selected from the group consisting of 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 above polyimide precursor composition may further include a solvent. The solvent may be an aprotic polar organic solvent, and specifically may include at least one selected from the group consisting of N,N'-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N,N'-dimethylformamide (DMF), dimethylsulfoxide (DMSO), diethylacitamide (DEAc), N-ethyl-2-pyrrolidone (NEP), N,N'-diethylformamide (DEF), dimethylpropanamide (DMPA), and gamma-butyrolactone (GBL).

[0028] The above polyimide precursor composition may further include a dehydrating condensing agent. The dehydrating condensing agent may include, for example, at least one selected from the group consisting of 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'-disuccinimidylcarbonate.

[0029] The above polyimide precursor may include a polyamic acid ester and a polyamic acid.

[0030] The polyimide precursor composition may have a weight average molecular weight of 1,000 g / mol to 100,000 g / mol. The lower limit of the weight average molecular weight may be 1,500 g / mol, 2,000 g / mol, 2,500 g / mol, or 3,000 g / mol or more, and the upper limit of the weight average molecular weight may 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 less. The weight average molecular weight may be measured by gel permeation chromatography (GPC) analysis using N-methyl-2-pyrrolidone (NMP) as a solvent.

[0031] Method for producing a polyimide precursor composition

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

[0033] The above polyimide precursor may include a polyamic acid ester and a polyamic acid.

[0034] Specifically, conventional polyimide precursor compositions have a problem in that they are difficult to use as negative polyimide precursors over time after production due to the imidization reaction (ring closure) that occurs due to the catalyst (e.g., pyridine, etc.) used in the production of the polyimide precursor. The present invention suppresses the ring closure rate of the polymer by using an acid having one or more carboxyl groups in the molecule, thereby producing a polyimide precursor composition with excellent storage stability.

[0035] The acid having one or more carboxyl groups in the molecule may be used in an amount of 0.5 to 1.5 molar equivalents per 1 molar equivalent of the polyimide precursor. For example, the upper limit may be 1.5, 1.4, 1.3, 1.2, 1.1 molar equivalents or less, and the lower limit may be 0.5, 0.6, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95 molar equivalents or more. If the acid having one or more carboxyl groups in the molecule is used in an amount less than 0.5 molar equivalents, the storage stability of the manufactured polyimide precursor composition is deteriorated, which is undesirable, and if it is used in an amount exceeding 1.5 molar equivalents, the properties of the polyimide precursor composition are deteriorated due to hydrolysis, or the storage stability efficiency is not increased, which is inefficient, which is undesirable.

[0036] The above step (a) may be a step of preparing a reactant by mixing (a-1) an dianhydride monomer and an alcohol compound having an unsaturated double bond, and then polymerizing the reactant and a diamine monomer to prepare a polyimide precursor.

[0037] The above step (a) may be a step of producing a polyamic acid by polymerizing (a-2) an dianhydride monomer and a diamine monomer, and then reacting an alcohol compound having an unsaturated double bond to produce a polyimide precursor.

[0038] The alcohol compound having the unsaturated double bond may be used in an amount of 2 to 3 molar equivalents relative to 1 molar equivalent of the dianhydride monomer. For example, the upper limit may be 2.8, 2.7, 2.6, 2.55, 2.5, 2.45, 2.4, 2.35, 2.3 molar equivalents or less, and the lower limit may be 2.03, 2.05, 2.07, 2.08, 2.09, 2.1 molar equivalents or more. If the alcohol compound having the unsaturated double bond is used in an amount of less than 2 molar equivalents, there is a high possibility that a polyimide precursor composition having excellent negative characteristics will not be produced, which is not preferred, and if it is used in an amount exceeding 3 molar equivalents, the amount of the polyimide precursor composition produced does not increase relative to the content of the alcohol compound used, which is economically inefficient, which is not preferred.

[0039] In the method for manufacturing the above polyimide precursor composition, step (b) may additionally include a step of purifying, filtering, and drying after mixing the polyimide precursor and an acid having at least one carboxyl group in the molecule.

[0040] An acid having one or more carboxyl groups in the molecule may not be removed from the polyimide precursor by the purification, filtration and drying.

[0041] The above purification may include a purification method commonly used in polymer synthesis, such as reprecipitation, such as an alcohol precipitation method.

[0042] Photosensitive resin composition

[0043] The present invention provides a photosensitive resin composition comprising the polyimide precursor composition. The photosensitive resin composition according to the present invention may be a negative photosensitive resin composition.

[0044] Specifically, the photosensitive resin composition may include additives that can be commonly used in the technical field of photosensitive resin compositions, such as a photoinitiator, a crosslinking agent, and a surfactant.

[0045] The polyimide precursor composition according to the present invention has the effect of suppressing the conversion rate and providing excellent storage stability by including an acid having one or more carboxyl groups in the molecule.

[0046] Figure 1 shows the results of H-NMR measurement of a polyimide precursor composition manufactured according to Example 1-1.

[0047] Figure 2 shows the results of H-NMR measurement of a polyimide precursor composition manufactured according to Example 1-2.

[0048] Figure 3 shows the results of H-NMR measurement of a polyimide precursor composition manufactured according to Comparative Example 1-1.

[0049] To aid in understanding the present invention, examples are presented. The following examples are provided solely to facilitate a better understanding of the present invention, and the scope of the present invention is not limited by the examples.

[0050] <Example 1: Preparation of polyimide precursor composition>

[0051] Example 1-1

[0052] A BPDA-ODPA-HEMA solution was synthesized by stirring 30 mol% of dianhydride (BPDA), 70 mol% of oxydiphthalic dianhydride (ODPA), 210 mol% of 2-hydroxyethyl methacrylate (HEMA), and 100 mol% of pyridine in a reactor in a gamma-butyrolactone (GBL) solvent at room temperature for more than 10 hours.

[0053] The above BPDA-ODPA-HEMA solution was stirred for 30 minutes after adding 202 mol% of dicyclohexylcarbodiamine (DCC) at a temperature of -10°C. Thereafter, 98 mol% of 4,4'-diaminodiphenyl ether (4,4'-ODA) was added, the temperature was raised to room temperature, and the mixture was stirred for 2 hours to prepare a polyimide precursor.

[0054] 100 mol% of mandelic acid was added to the polyimide precursor manufactured above, stirred for 1 hour, filtered to separate, and then precipitated in 2 to 4 times the weight of ethanol to remove unreacted substances. The obtained precipitate was redissolved in gamma-butyrolactone (GBL), and the redissolved solution was precipitated in 8 to 10 times the weight of ultrapure water and dried to obtain the final polyimide precursor composition.

[0055] Examples 1-2 to 1-6

[0056] A polyimide precursor composition was prepared in the same manner as in Example 1-1, except that the type of acid having one or more carboxyl groups in the molecule was used differently, as shown in Table 1 below.

[0057] Comparative Example 1-1

[0058] A polyimide precursor composition was prepared in the same manner as in Example 1-1, except that mandelic acid was not used instead of mandelic acid in Example 1-1.

[0059]

[0060] Table 1 below shows the types and contents of monomers used in preparing polyimide precursor compositions according to Examples 1-1 to 1-6 and Comparative Example 1-1.

[0061] Classification Anhydride monomer Diamine monomer Alcohol compound having unsaturated double bond Acid having one or more carboxyl groups in the molecule Example 1-1 BPDA (30 mol%) ODPA (70 mol%) ODA (98 mol%) HEMA (210 mol%) Mandelic acid (100 mol%) Example 1-2 BPDA (30 mol%) ODPA (70 mol%) ODA (98 mol%) HEMA (210 mol%) Oxalic acid (100 mol%) Example 1-3 BPDA (30 mol%) ODPA (70 mol%) ODA (98 mol%) HEMA (210 mol%) Succinic acid (100 mol%) Example 1-4 BPDA (30 mol%) ODPA (70 mol%) ODA (98 mol%) HEMA (210 mol%) Citric acid (100 mol%) Example 1-5 BPDA (30 mol%) ODPA (70 mol%) ODA (98 mol%) mol%)HEMA (210 mol%)Acetic acid (100 mol%)Example 1-6BPDA (30 mol%)ODPA (70 mol%)ODA (98 mol%)HEMA (210 mol%)Malic acid (100 mol%)Comparative Example 1-1BPDA (30 mol%)ODPA (70 mol%)ODA (98 mol%)HEMA (210 mol%)-

[0062]

[0063] <Example 2: Preparation of photosensitive resin composition>

[0064] Example 2-1

[0065] A polyimide precursor composition and a photoinitiator prepared according to Example 1-1 were mixed in an organic solvent, and filtered through a filter to prepare a negative photosensitive resin composition.

[0066] Examples 2-2 to 2-6

[0067] A photosensitive resin composition was prepared in the same manner as in Example 2-1, except that the polyimide precursor compositions prepared in Examples 1-2 to 1-6 were used instead of the polyimide precursor composition prepared in Example 1-1.

[0068]

[0069] <Experimental Example: Evaluation of the Characteristics of Polyimide Precursor Compositions>

[0070] Experimental Example 1: Measurement of weight-average molecular weight (Mw)

[0071] The polyimide precursor compositions manufactured according to Examples 1-1 to 1-6 and Comparative Example 1-1 were subjected to GPC (Gel Permeation Chromatography) analysis using N-methyl-2-pyrrolidone (NMP) as a solvent to measure the weight average molecular weight, and the results are shown in Table 2 below.

[0072] Experimental Example 2: Measurement of the Closing Rate

[0073] The conversion rate of the polyimide precursor compositions manufactured according to Examples 1-1 to 1-6 and Comparative Example 1-1 was measured through H-NMR.

[0074] FIG. 1 shows the results of H-NMR measurement of a polyimide precursor composition manufactured according to Example 1-1, FIG. 2 shows the results of H-NMR measurement of a polyimide precursor composition manufactured according to Example 1-2, and FIG. 3 shows the results of H-NMR measurement of a polyimide precursor composition manufactured according to Comparative Example 1-1.

[0075] As a result of H-NMR measurement of the polyimide precursor composition (Figs. 1 to 3), when 7 ppm is taken as 1 at the peak of 7 to 7.1 ppm on the x-axis, it can be confirmed that the integration value of 7.1 ppm gradually increases as the ring closure rate increases. This is due to the shift of the benzene peak of the ODA portion within the molecular structure as the ring closure progresses, and this can be used to infer that the ring closure occurred during the reaction.

[0076] The conversion rate was calculated using the H-NMR measurement results and Equation 1 below. More specifically, the conversion rate was measured twice in total: after polymerization and drying (conversion rate A) and after the storage stability test of Experimental Example 3 below (conversion rate B), and the results are shown in Table 2 below.

[0077] [Formula 1]

[0078] Exchange rate (%) = I B / (I A + I B ) X 100

[0079] In equation 1,

[0080] I A is the 7.0 ppm integral value from the H-NMR measurement results,

[0081] I B is the 7.1 ppm integral value from the H-NMR measurement results.

[0082] Experimental Example 3: Storage Stability Verification

[0083] The polyimide precursor compositions manufactured according to Examples 1-1 to 1-6 and Comparative Example 1-1 were each dissolved in 35% gamma-butyrolactone (GBL) and then left in an oven at 60°C for 5 days. The results are shown in Table 2 below according to the criteria below.

[0084] A: The increase in the exchange rate is less than 10%

[0085] B: The increase in the exchange rate is 10% or more but less than 20%.

[0086] C: The increase in the exchange rate is 20% or more

[0087] D: Not measurable

[0088] Experimental Example 4: Haze Measurement

[0089] After the storage stability test according to Experimental Example 3 above, the turbidity of the solution was measured using a Haze meter, and the results are shown in Table 2 below.

[0090]

[0091] Table 2 below summarizes the molecular weight, conversion rate, storage stability, and Haze measurement results of the polyimide precursor compositions manufactured according to Examples 1-1 to 1-6 and Comparative Example 1-1.

[0092] Classification Example 1-1 Example 1-2 Example 1-3 Example 1-4 Example 1-5 Example 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 Exchange rate A (%) 17.35 14.52 18.69 21.25 27.53 20.63 20.63 Exchange rate B (%) 25.06 26.07 20.63 48.71 34.64 46.80 - Storage stability ABACBCDHaze (%) 0.27 0.31 0.21 82.93 79.17 93.59 Not measurable

[0093]

[0094] According to Table 2, it can be confirmed that Examples 1-1 to 1-6, which include acids having one or more carboxyl groups in the molecule (Ex. mandelic acid, oxalic acid, succinic acid, citric acid, acetic acid, malic acid), have higher storage stability than Comparative Example 1-1, which does not include acids having one or more carboxyl groups in the molecule.

[0095] In addition, it can be confirmed that the polyimide precursor compositions of Examples 1-1 to 1-6 maintain a low conversion rate.

[0096] Meanwhile, it can be confirmed in Table 2 that the polyimide precursor composition of Comparative Example 1-1 has a storage stability of D (not measurable). In order to measure the ring closure rate, a step of dissolving in a DMSO-d6 solvent must be performed in NMR equipment, but the polyimide precursor composition of Comparative Example 1-1 did not dissolve in the DMSO-d6 solvent as the imidization reaction (ring closure) progressed during the storage stability test, making NMR measurement impossible. Therefore, the ring closure rate B could not be measured, and the storage stability was also not measurable (D).

[0097] Meanwhile, according to Table 2, while the polyimide precursor compositions of Examples 1-1 to 1-6 were capable of haze measurement, the polyimide precursor composition of Comparative Example 1-1 was not capable of haze measurement. This is because the polyimide precursor composition of Comparative Example 1-1 was gelated as the imidization reaction (ring closure) progressed. Through this, it was confirmed that the polyimide precursor composition according to the present invention had excellent storage stability.

[0098]

[0099] The specification omits detailed descriptions of matters that would be readily apparent and inferred by those skilled in the art. Furthermore, various modifications, other than the specific examples described herein, are possible without altering the technical spirit or essential configuration of the invention. Therefore, the present invention may be practiced in ways other than those specifically described and exemplified herein, as will be readily apparent to those skilled in the art.

Claims

1. A polyimide precursor comprising an dianhydride monomer, a diamine monomer, and an alcohol compound having an unsaturated double bond as polymerization units; and An acid having one or more carboxyl groups in the molecule; A polyimide precursor composition comprising:

2. In paragraph 1, A polyimide precursor composition, wherein the above polyimide precursor composition is a negative polyimide precursor composition.

3. In paragraph 1, A polyimide precursor composition, wherein the acid having at least one carboxyl group in the molecule comprises 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.

4. In paragraph 1, The above dianhydride monomers are biphenyl tetracarboxylic dianhydride (BPDA), oxydiphthalic dianhydride (ODPA), pyromellitic dianhydride (PMDA), 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), diphenylsulfone-3,4,3',4'-tetracarboxylic dianhydride (DSDA), bis(3,4-dicarboxyphenyl)sulfide dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2,2-Bis(3,4-dicarboxyphenyl)propane dianhydride, p-phenylenebis(trimellitic monoester acid anhydride), p-biphenylenebis(trimellitic monoester acid anhydride), m-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, p-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2-bis〔(3,4-dicarboxy phenoxy)phenyl〕propane dianhydride (BPADA), 2,3,6,7-naphthalene tetracarboxylic acid A polyimide precursor composition comprising at least one selected from the group consisting of dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and 4,4'-(2,2-hexafluoroisopropylidene)diphthalic acid dianhydride.

5. In paragraph 4, A polyimide precursor composition, wherein the above dianhydride monomer comprises biphenyltetracarboxylic acid dianhydride (BPDA) and oxydiphthalic dianhydride (ODPA).

6. In paragraph 4, A polyimide precursor composition, wherein the content of biphenyltetracarboxylic acid dianhydride (BPDA) among the total dianhydride monomers is greater than 0 mol% and less than or equal to 50 mol%.

7. In paragraph 4, A polyimide precursor composition, wherein the content of oxydiphthalic dianhydride (ODPA) among the total dianhydride monomers is 50 mol% or more and less than 100 mol%.

8. In paragraph 1, The above diamine monomers are 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 (m-tolidine), 2,2-bisaminophenoxyphenylpropane (BAPP), metaphenylenediamine, 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'-diaminobenzanilide, 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 sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 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'-Diaminodiphenylsulfoxide, 3,4'-Diaminodiphenylsulfoxide, 4,4'-Diaminodiphenylsulfoxide, 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-aminophenylsulfide)benzene, 1,3-bis(4-aminophenylsulfide)benzene, 1,4-bis(4-aminophenylsulfide)benzene, 1,3-bis(3-aminophenylsulfone)benzene, 1,3-bis(4-aminophenylsulfone)benzene, 1,4-bis(4-aminophenylsulfone)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〕ketone, bis〔3-(4-aminophenoxy)phenyl〕ketone, bis〔4-(3-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〕sulfone, bis〔3-(4-aminophenoxy)phenyl〕sulfone, bis〔4-(3-aminophenoxy)phenyl〕sulfone, bis〔4-(4-aminophenoxy)phenyl〕sulfone, bis〔3-(3-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, 2,2-bis〔4-(3-aminophenoxy)phenyl〕propane, 2,2-bis〔3-(3-aminophenoxy)phenyl〕-1,1,1,3,3,3-hexafluoropropane, 2,2-bis〔3-(4-aminophenoxy)phenyl〕-1,1,1,3,3,3-hexafluoropropane, 2,A polyimide precursor composition comprising at least one selected from the group consisting of 2-bis〔4-(3-aminophenoxy)phenyl〕-1,1,1,3,3,3-hexafluoropropane and 2,2-bis〔4-(4-aminophenoxy)phenyl〕-1,1,1,3,3,3-hexafluoropropane.

9. In paragraph 1, A polyimide precursor composition, wherein the alcohol compound having the unsaturated double bond 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.

10. A photosensitive resin composition comprising a polyimide precursor composition according to paragraph 1. 11.(a) a step of preparing a polyimide precursor by polymerizing an dianhydride monomer, a diamine monomer, and an alcohol compound having an unsaturated double bond; and (b) a step of preparing a polyimide precursor composition by mixing the polyimide precursor and an acid having at least one carboxyl group in the molecule; A method for producing a polyimide precursor composition comprising:

12. In paragraph 11, A method for producing a polyimide precursor composition, wherein an acid having at least one carboxyl group in the molecule is used in an amount of 0.5 to 1.5 molar equivalents per 1 molar equivalent of the polyimide precursor.

13. In paragraph 11, A method for producing a polyimide precursor composition, wherein the step (a) is a step of producing a reactant by mixing (a-1) an dianhydride monomer and an alcohol compound having an unsaturated double bond, and then polymerizing the reactant and a diamine monomer to produce a polyimide precursor.

14. In paragraph 11, A method for producing a polyimide precursor composition, wherein the step (a) is a step of producing a polyamic acid by polymerizing (a-2) an dianhydride monomer and a diamine monomer, and then reacting the polyamic acid with an alcohol compound having an unsaturated double bond to produce a polyimide precursor.

15. In paragraph 11, A method for producing a polyimide precursor composition, wherein the alcohol compound having the above unsaturated double bond is used in an amount of 2 to 3 molar equivalents per 1 molar equivalent of the above dianhydride monomer.

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