Photosensitive resin composition, insulation film, and semiconductor device

Abstract

The purpose of the present invention is to provide a photosensitive resin composition, an insulation film, and a semiconductor device, comprising a polyimide resin.

Description

Photosensitive resin composition, insulating film and semiconductor device

[0001] This application relates to a photosensitive resin composition, an insulating film, and a semiconductor device. Specifically, it relates to a photosensitive resin composition, an insulating film, and a semiconductor device comprising a polyimide resin. This application claims the benefit of Korean Patent Application No. 10-2023-0123315, filed with the Korean Intellectual Property Office on September 15, 2023, the entire contents of which are incorporated herein by reference.

[0002] Interlayer insulating films or surface protective films of semiconductor devices require excellent mechanical properties and high heat resistance, and thus polyimide-based binder resins with excellent properties are used.

[0003] Along with the expansion of the application of miniaturization technology in the FAB (Fabrication) process, packaging technology is also undergoing significant changes to process technology for manufacturing high-performance, thin, and compact packages.

[0004] With the recent growth of the fan-out wafer-level packaging (FO-WLP) market due to changes in semiconductor post-processing technology, the demand for photosensitive polyimide (PSPI) for redistribution layer (RDL) that can be cured at low temperatures and has excellent physical properties is growing significantly.

[0005] In the case of negative type photosensitive polyimide, mechanical properties are relatively excellent, but it is difficult to achieve high resolution. In the case of positive type photosensitive polyimide, relatively high resolution is possible, but it is difficult to satisfy the mechanical properties.

[0006] Accordingly, there is a need for the development of a photosensitive polyimide material that satisfies both high resolution and mechanical properties.

[0007] Specifically, as a reliability evaluation of an insulating film manufactured including the photosensitive polyimide material, development of a method for deriving and evaluating factors that have a major influence on the reliability of the insulating film is required, and as the evaluation method, development of a high-reliability photosensitive resin composition and an insulating film including the same, which are included in a semiconductor device manufactured through a thermal cycle test (TC test), is required.

[0008] The present invention provides a photosensitive resin composition, an insulating film, and a semiconductor device including a polyimide resin.

[0009] However, the problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned can be clearly understood by those skilled in the art from the description below.

[0010] One embodiment of the present invention is a photosensitive resin composition containing a polyimide resin, wherein the photosensitive resin composition is cured to produce a film having a thickness of 10 ㎛, and when the thermal expansion coefficient, Young's modulus, tensile strength and elongation at break of the film are measured, I according to the following formula 1 TC A photosensitive resin composition having a value of 1000 or more is provided.

[0011] [Formula 1]

[0012] I TC = [(Y 2 ×T×E) / (CC Cu )]

[0013] Above I TC is the thermal cycle indicator of the above film,

[0014] The above Y is the Young's modulus of the film,

[0015] The above T is the tensile strength of the film,

[0016] The above E is the elongation at break of the film,

[0017] The above C is the coefficient of thermal expansion of the film,

[0018] C above Cu is the coefficient of thermal expansion of copper.

[0019] One embodiment of the present invention provides an insulating film comprising the photosensitive resin composition or a cured product thereof.

[0020] One embodiment of the present invention provides a semiconductor device including the insulating film.

[0021] A photosensitive resin composition according to one embodiment of the present invention can form an insulating film having excellent elongation, sensitivity, and / or adhesion to a substrate, and can provide a photosensitive resin composition capable of forming a highly reliable insulating film in a simpler manner by measuring predetermined physical properties of a film sample and calculating evaluation factors.

[0022] A photosensitive resin composition according to one embodiment of the present invention may exhibit excellent mechanical properties (e.g., high elongation, substrate adhesion, low sensitivity, etc.) as a photosensitive material without modification of a crosslinkable polymer, and may be capable of fine pattern development.

[0023] An insulating film and a semiconductor device according to one embodiment of the present invention include the photosensitive resin composition having high elongation, low sensitivity, and excellent adhesion to a substrate, and therefore, warping of a wafer in a semiconductor device using the insulating film can be suppressed and reliability can be excellent.

[0024] The effects of the present invention are not limited to the effects described above, and effects not mentioned will be clearly understood by those skilled in the art from the present specification and the attached drawings.

[0025] Throughout this specification, whenever a part is said to "include" a component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise specifically stated.

[0026] Throughout this specification, when it is said that an element is "on" another element, this includes not only cases where the element is in contact with the other element, but also cases where another element exists between the two elements.

[0027] Throughout this specification, the unit “parts by weight” may mean the weight ratio between each component.

[0028] Throughout this specification, “(meth)acrylate” is used to refer to both acrylate and methacrylate.

[0029] Throughout the present specification, the term “monomer unit” may mean a form in which a monomer is reacted within a polymer, and specifically may mean a form in which the monomer undergoes a polymerization reaction to form the backbone of the polymer, for example, a main chain or a side chain.

[0030] Throughout the present specification, the “weight average molecular weight” and “number average molecular weight” of a compound can be calculated using the molecular weight and molecular weight distribution of the compound. Specifically, a sample having a concentration of 1 wt% of the compound is prepared by adding tetrahydrofuran (THF) and the compound to a 1 ml glass bottle, and a standard sample (polystyrene) and the sample sample are filtered through a filter (pore size: 0.45 μm), and then injected into a GPC injector. The elution time of the sample sample is compared with the calibration curve of the standard sample, thereby obtaining the molecular weight and molecular weight distribution of the compound. At this time, Infinity II 1260 (Agilient) can be used as the measuring device, and the flow rate can be set to 1.00 mL / min and the column temperature to 40.0 °C.

[0031] One embodiment of the present invention is a photosensitive resin composition containing a polyimide resin, wherein the photosensitive resin composition is cured to produce a film having a thickness of 10 ㎛, and when the thermal expansion coefficient, Young's modulus, tensile strength and elongation at break of the film are measured, I according to the following formula 1 TC A photosensitive resin composition having a value of 1000 or more is provided.

[0032] [Formula 1]

[0033] I TC = [(Y 2 ×T×E) / (CC Cu )]

[0034] In the above equation 1,

[0035] Above I TC is the thermal cycle indicator of the above film,

[0036] The above Y is the Young's modulus of the film,

[0037] The above T is the tensile strength of the film,

[0038] The above E is the elongation at break of the film,

[0039] The above C is the coefficient of thermal expansion of the film,

[0040] C above Cu is the coefficient of thermal expansion of copper.

[0041] A photosensitive resin composition according to one embodiment of the present invention can form an insulating film having excellent elongation, sensitivity, and / or adhesion to a substrate, and can provide a photosensitive resin composition capable of forming a highly reliable insulating film in a simpler manner by measuring predetermined physical properties of a film sample and calculating evaluation factors.

[0042] The measurement values ​​of each property substituted into the above equation 1 may be determined by the composition of the photosensitive resin composition, curing conditions, etc.

[0043] Hereinafter, a method for measuring certain physical properties and calculating evaluation factors for a film sample of the photosensitive resin composition will be described in more detail.

[0044] [Method for calculating physical property measurements and evaluation factors]

[0045] A photosensitive resin composition including a polyimide resin according to one embodiment of the present invention is characterized by a temperature cycle evaluation factor (I TC, The Thermal Cycle Indicator) value may be greater than 1000.

[0046] In one embodiment of the present invention, the thermal cycle evaluation factor (Thermal Cycle Indicator) may be derived by curing a photosensitive resin composition including a polyimide resin to produce a film sample having a thickness of 10 μm and measuring the physical properties thereof.

[0047] In one embodiment of the present invention, the I TCis a thermal cycle indicator of the film, and may mean a value calculated by measuring a predetermined property value included in Equation 1 for a film sample manufactured for evaluating the photosensitive resin composition, and using the measured property value.

[0048] By comparing the above temperature cycle evaluation factor values, a photosensitive resin composition having excellent elongation, sensitivity, and / or adhesion to a substrate and capable of forming a highly reliable insulating film can be provided in a simpler manner.

[0049] Specifically, the temperature cycle evaluation factor (I TC ) may be classified as a good product if the film has a desirable range, and the photosensitive resin composition used to manufacture the film classified as a good product, i.e., the film sample, may be evaluated as a good product.

[0050] In one embodiment of the present invention, the temperature cycle evaluation factor (I TC ) may be 1000 or more. Specifically, the temperature cycle evaluation factor may be 1100 or more, 1200 or more, 1300 or more, 1400 or more, 1500 or more, 1600 or more, 1700 or more, 1800 or more, 1900 or more, or 2000 or more.

[0051] In one embodiment of the present invention, the temperature cycle evaluation factor (I TC ) may be less than or equal to 4000. Specifically, the temperature cycle evaluation factor (I TC ) may be 3900 or less, 3800 or less, 3700 or less, 3600 or less, 3500 or less, 3400 or less, 3300 or less, 3200 or less, 3100 or less, or 3000 or less.

[0052] In one embodiment of the present invention, the temperature cycle evaluation factor (I TC) may be a unitless value. Specifically, it may be a value without a separate unit, which is a result value calculated by dividing the measurement value of each property included in the above equation 1 by the standard unit of each property and then substituting it.

[0053] Here, the standard unit of each property is, Y is the Young's modulus (GPa) of the film, T is the tensile strength (Mpa) of the film, E is the breaking elongation (%) of the film, C is the thermal expansion coefficient (ppm / ℃) of the film, and C Cu may be the coefficient of thermal expansion of copper (ppm / ℃).

[0054] In other words, the measurement values ​​of each property substituted into the above equation 1 are, where Y is the Young's modulus of the film / (GPa), T is the tensile strength of the film / (Mpa), E is the breaking elongation of the film / (%), C is the thermal expansion coefficient of the film / (ppm / ℃), and C Cu can be the coefficient of thermal expansion of copper / (ppm / ℃).

[0055] That is, the measured value of each property included in the above formula 1 may mean only the numerical value excluding the unit from the value converted to the standard unit of each property by converting the measured value of each property. For example, the thermal expansion coefficient of the copper may be 17 ppm / ℃, and in the above formula 1, the C Cu could be 17.

[0056] Temperature cycle evaluation factor (I) of the above film TC ) If the value satisfies the above-mentioned range, the photosensitive resin composition used to manufacture the film sample may be evaluated as a good product, and through the evaluation, a photosensitive resin composition having excellent elongation, sensitivity, and / or adhesion to a substrate and capable of forming a highly reliable insulating film may be provided.

[0057] In one embodiment of the present invention, the film is manufactured by applying a photosensitive resin composition containing a polyimide resin to a substrate to form a coating film and then curing the coating film, and may be a film sample manufactured for evaluating the photosensitive resin composition. The method for applying the resin composition containing the polyimide resin to the substrate is not particularly limited, and for example, methods such as screen printing, offset printing, flexographic printing, and inkjet printing may be used.

[0058] In one embodiment of the present invention, the curing may be performed under a temperature condition of 160°C or higher and 240°C or lower. Specifically, the curing may be performed under a temperature condition of 170°C or higher, 180°C or higher, 190°C or higher, or 200°C or higher, and may be performed under a temperature condition of 230°C or lower, 220°C or lower, 210°C or lower, or 200°C or lower. For example, the curing may be performed under a temperature condition of 200°C for a predetermined time, for example, 1 hour, but is not limited thereto.

[0059] In one embodiment of the present invention, the curing may further include preliminary curing, and the preliminary curing may be performed under a temperature condition of 90° C. or higher and 120° C. or lower. Specifically, the preliminary curing may be performed under a temperature condition of 95° C. or higher, 100° C. or higher, or 105° C. or higher, and may be performed under a temperature condition of 115° C. or lower, 110° C. or lower, or 105° C. or lower. For example, the preliminary curing may be performed under a temperature condition of 105° C. for a predetermined time, for example, 120 seconds, but is not limited thereto. The preliminary curing may be performed to secure fairness before the curing.

[0060] In one embodiment of the present invention, the curing may be performed by irradiating light having a wavelength of 250 nm to 450 nm. Specifically, the curing may be performed by irradiating light having a wavelength of 260 nm, 270 nm, 280 nm, 290 nm, or 300 nm, and may be performed by irradiating light having a wavelength of 440 nm, 430 nm, 420 nm, 410 nm, 400 nm, or 300 nm. In addition, as described below, the light irradiation may be performed using a light source such as a mercury vapor arc, a carbon arc, or a Xe arc. For example, in the case of a negative type photosensitive resin composition, the curing may be performed using an i-line stepper of 200 mJ / cm2 to 900 mJ / cm2, but is not limited thereto. Meanwhile, in the case of a positive type photosensitive resin composition, the above curing may be performed by controlling the temperature conditions described above without separate light irradiation.

[0061] In one embodiment of the present invention, the thickness of the film may be 9 ㎛ or more and 11 ㎛ or less. Specifically, the thickness of the film may be 9 ㎛ or more and 10 ㎛ or less or 10 ㎛ or more and 11 ㎛ or less, and preferably 10 ㎛. In other words, the thickness of the film sample manufactured for evaluating the photosensitive resin composition may be 10±1 ㎛. The thickness of the film sample may have an error depending on the curing method and the measuring method, but when it increases or decreases by a certain value, the physical properties measured in the polyimide film may also change by a certain value.

[0062] In one embodiment of the present invention, the Young's modulus may be measured by producing a sample having a size of 10 mm × 100 mm and a thickness of 10 ㎛ for a film sample manufactured for evaluation of the photosensitive resin composition, and measuring it under room temperature and a speed of 5 mm / min using a UTM (Universal Testing Machine).

[0063] In one embodiment of the present invention, the tensile strength of the film may be measured by producing a sample of 10 mm × 100 mm in size and 10 ㎛ in thickness for a film sample manufactured for evaluation of the photosensitive resin composition, and measuring it under room temperature and a speed of 5 mm / min using a UTM (Universal Testing Machine).

[0064] In one embodiment of the present invention, the elongation at break of the film may be measured by producing a sample of 10 mm × 100 mm in size and 10 ㎛ in thickness for a film sample manufactured for evaluation of the photosensitive resin composition, and measuring it under room temperature and 5 mm / min speed conditions using a UTM (Universal Testing Machine).

[0065] In one embodiment of the present invention, the coefficient of thermal expansion (CTE) may be measured using a thermal expansion coefficient measuring device at a temperature of 50°C or more and 100°C or less. Specifically, the coefficient of thermal expansion (CTE) may be, but is not limited to, the thermal expansion change pattern measured using TMA (Q400 Co.) when a first temperature increasing process is performed at a temperature increasing rate of 1 ℃ / min to 15 ℃ / min or more, or 5 ℃ / min to 10 ℃ / min or less in a temperature range of 50 ℃ to 100 ℃, while setting the pulling force of the film sample to 0.01 N or more and 0.1 N or less, or 0.01 N or more and 0.05 N or less, and cooling is performed at a cooling rate of 1 ℃ / min to 15 ℃ / min or more, or 5 ℃ / min to 10 ℃ / min or less in a temperature range of 100 ℃ to 50 ℃, after which the film sample is cooled.

[0066] [Photosensitive resin composition]

[0067] One embodiment of the present invention is a photosensitive resin composition containing a polyimide resin, wherein the photosensitive resin composition is cured to produce a film having a thickness of 10 ㎛, and when the thermal expansion coefficient, Young's modulus, tensile strength and elongation at break of the film are measured, I according to the above-mentioned formula 1 TC A photosensitive resin composition having a value of 1000 or more is provided.

[0068] The photosensitive resin composition according to one embodiment of the present invention is characterized by measuring a predetermined physical property of a film sample and calculating an evaluation factor, thereby determining the temperature cycle evaluation factor (I). TC) may be evaluated as a good product having the above-described range, and accordingly, the photosensitive resin composition used to manufacture the film evaluated as a good product, i.e., the film sample, may be evaluated as a good product. The photosensitive resin composition evaluated as a good product may have excellent elongation, sensitivity, and / or adhesion to a substrate, and may be capable of forming a highly reliable insulating film.

[0069] In one embodiment of the present invention, the coefficient of thermal expansion, Young's modulus, tensile strength, and elongation at break of the film may be measured for a film having a thickness of 10 ㎛ manufactured by curing the photosensitive resin composition, i.e., a film sample manufactured for evaluating the photosensitive resin composition. The manufacturing of the film, measurement of the coefficient of thermal expansion, Young's modulus, tensile strength, and elongation at break may be the same as described above for the evaluation method of the film, and the measured values ​​of each property substituted into the above formula 1 may mean only a numerical value obtained by excluding the unit from a value converted into a standard unit of each property.

[0070] The film may have a thermal expansion coefficient of 30 ppm / ℃ or more and 80 ppm / ℃ or less, measured in a temperature range of 50°C or more and 100°C or less. Specifically, the film sample may have a thermal expansion coefficient of 32 ppm / ℃ or more, 34 ppm / ℃ or more, 36 ppm / ℃ or more, 38 ppm / ℃ or more, or 40 ppm / ℃ or more, and may be 78 ppm / ℃ or less, 76 ppm / ℃ or less, 74 ppm / ℃ or less, 72 ppm / ℃ or less, or 70 ppm / ℃ or less, measured using a thermal expansion coefficient measuring device while heating and cooling at a temperature of 50°C or more and 100°C or less. The thermal expansion coefficient may be implemented because the film includes a polyimide resin described below.

[0071] When the film has a coefficient of thermal expansion within the aforementioned range, the heat resistance can be improved by alleviating deformation due to heat of an insulating film including the photosensitive resin composition, and the substrate of a semiconductor device including the film can be prevented from being damaged by heat during heat treatment of a metal thin film formed on a substrate, and the phenomenon of warpage occurring in the metal thin film formed on the substrate can also be suppressed.

[0072] The film may have a Young's modulus of 2.2 GPa or more and 4.0 GPa or less. Specifically, the film may have a Young's modulus of 2.3 MPa or more, 2.4 GPa or more, 2.5 GPa or more, 2.6 GPa or more, 2.7 GPa or more, 2.8 GPa or more, 2.9 GPa or more, or 3.0 GPa or more, or 3.9 GPa or less, 3.8 GPa or less, 3.7 GPa or less, 3.6 GPa or less, or 3.5 GPa or less. The Young's modulus may be realized by the film including a polyimide resin described below.

[0073] The film may have a tensile strength of 100 MPa or more and 200 MPa or less. Specifically, the film may have a tensile strength of 110 MPa or more, 120 MPa or more, 130 MPa or more, 140 MPa or more, or 150 MPa or more, or 190 MPa or less, 180 MPa or less, 170 MPa or less, 160 MPa or less, or 150 MPa or less. The tensile strength may be realized by the film including a polyimide resin described below.

[0074] The film may have an elongation at break of 40% or more and 100% or less. Specifically, the film may have an elongation at break of 45% or more, 50% or more, or 55% or more, and may have an elongation at break of 95% or less, 90% or less, or 85% or less. The elongation at break may be realized by the film including a polyimide resin described below.

[0075] When the above film has a Young's modulus, tensile strength and elongation at break within the aforementioned range, the properties required for an insulating film including the photosensitive resin composition can be realized.

[0076] In one embodiment of the present invention, the photosensitive resin composition may further include a photoinitiator. Specifically, the photoinitiator is a substance that initiates crosslinking and / or curing reaction of the photosensitive resin upon exposure to light, and any conventional photoinitiator may be used without limitation. In view of polymerization characteristics, initiation efficiency, absorption wavelength, availability, price, etc., at least one compound selected from the group consisting of acetophenone compounds, benzophenone compounds, triazine compounds, biimidazole compounds, oxime compounds, and thioxanthone compounds may be used.

[0077] Specific examples of the above acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, etc.

[0078] Examples of the above benzophenone compounds include benzophenone, 0-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc.

[0079] Specific examples of the above triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, Examples include 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, etc.

[0080] Specific examples of the above biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4'5,5'-tetraphenyl-1,2'-biimidazole, or imidazole compounds in which the phenyl group at the 4,4',5,5' position is substituted by a carboalkoxy group. Among these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(2,6-dichlorophenyl)-4,4'5,5'-tetraphenyl-1,2'-biimidazole are preferably used.

[0081] Specific examples of the above oxime compounds include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and representative commercial products include BASF's OXE-01 and OXE-02.

[0082] Examples of the above thioxanthone compounds include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, etc.

[0083] According to one embodiment of the present invention, the photoinitiator may preferably be an oxime ester photoradical initiator, and OXE-01, OXE-03, OXE-04, SPI-03, SPI-07, I367, etc. may be used, but are not limited thereto.

[0084] A photosensitive resin composition according to one embodiment of the present invention may include a polyimide resin and further include a photoacid generator.

[0085] According to one embodiment of the present invention, the photoacid generator is for the photosensitive resin composition to function as a chemical amplification type composition, and can effectively control the acid diffusion length, thereby improving the resolution of the pattern, etc. The photoacid generator may be any conventional photoacid generator without limitation, and preferably, an ionic photoacid generator, a sulfonyldiazomethane type, an N-sulfonyloxyimide type, a benzoin sulfonate type, a nitrobenzyl sulfonate type, a sulfone type, a glyoxime type, a triazine type, etc. can be used.

[0086] In one embodiment of the present invention, the photoacid generator may be a sulfonium salt, an iodonium salt, an ionic photoacid generator, sulfonyldiazomethane, an N-sulfonyloxyimide compound, a benzoinsulfonate compound, a pyrogallol trisulfonate compound, a nitrobenzylsulfonate compound, a sulfone compound, a glyoxime derivative compound, and a combination thereof.

[0087] The above sulfonium salt is a salt of a sulfonium cation and a sulfonate (sulfonic acid anion), and the sulfonium cation includes triphenolsulfonium, (4-tert-butoxyphenyl)diphenylsulfonium, bis(4-tert-butoxyphenyl)phenylsulfonium, 4-methylphenyldiphenylsulfonium, tris(4-methylphenylsulfonium), 4-tert-butylphenyldiphenylsulfonium, tris(4-tert-butylphenyl)sulfonium, tris(4-tert-butoxyphenyl)sulfonium, (3-tert-butoxyphenyl)diphenylsulfonium, bis(3-tert-butoxyphenyl)phenylsulfonium, tris(3-tert-butoxyphenyl)sulfonium, (3,4-di-tert-butoxyphenyl)diphenylsulfonium, Bis(3,4-di-tert-butoxyphenyl)phenylsulfonium, tris(3,4-di-tert-butoxyphenyl)sulfonium, diphenyl(4-thiophenoxyphenyl)sulfonium, (4-tert-butoxycarbonylmethyloxyphenyl)diphenylsulfonium, tris(4-tert-butoxycarbonylmethyloxyphenyl)sulfonium, (4-tert-butoxyphenyl)bis(4-dimethylaminophenyl)sulfonium, tris(4-dimethylaminophenyl)sulfonium, dimethyl-2-naphthyldiphenylsulfonium, dimethyl-2-naphthylsulfonium, 4-hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, diphenylmethylsulfonium, methyl-2-oxopropylphenylsulfonium, 2-oxocyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium and There are tribenzylsulfonium, etc., and the sulfonates include trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, and methanesulfonate.

[0088] The above iodonium salt is a salt of an iodonium cation and a sulfonate, and the iodonium cation includes diphenyliodonium, bis(4-tert-butylphenyl)iodonium, 4-tert-butoxyphenylphenyliodonium, and 4-methoxyphenylphenyliodonium.

[0089] The above sulfonyldiazomethane photoacid generators include bissulfonyldiazomethanes such as bis(ethylsulfonyl)diazomethane, bis(1-methylpropylsulfonyl)diazomethane, bis(2-methylpropylsulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(perfluoroisopropylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(4-methylphenylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, and bis(2-naphthylsulfonyl)diazomethane, 4-methylphenylsulfonylbenzoyldiazomethane, tert-butylcarbonyl-4-methylphenylsulfonyldiazomethane, There are sulfonylcarbonyldiazomethanes such as 2-naphthylsulfonylbenzoyldiazomethane, 4-methylphenylsulfonyl-2-naphthoyldiazomethane, methylsulfonylbenzoyldiazomethane, and tert-butoxycarbonyl-4-methylphenylsulfonyldiazomethane.

[0090] The above N-sulfonyloxyimide photoacid generators include succinic acid imide, naphthalenedicarboxylic acid imide, phthalic acid imide, cyclohexyldicarboxylic acid imide, 5-norbornene-2,3-dicarboxylic acid imide, 7-oxabicyclo[2,2,1]-5-heptene-2,3-dicarboxylic acid imide, trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, and methanesulfonate.

[0091] The above benzoin sulfonate photoacid generators include benzoin tosylate, benzoin mesylate, and benzoin butanesulfonate, and the above nitrobenzyl sulfonate photoacid generators include 2,4-dinitrobenzylsulfonate, 2-nitrobenzylsulfonate, 2,6-dinitrobenzylsulfonate, and compounds in which the nitro group of benzyl is substituted with a trifluoromethyl group. The above sulfone-based photoacid generators include bis(phenylsulfonyl)methane, bis(4-methylphenylsulfonyl)methane, bis(2-naphthylsulfonyl)methane, 2,2-bis(phenylsulfonyl)propane, 2,2-bis(4-methylphenylsulfonyl)propane, 2,2-bis(2-naphthylsulfonyl)propane, 2-methyl-2-(p-toluenesulfonyl)propionenone, 2-(cyclohexylcarbonyl)-2-(p-toluenesulfonyl)propane, and 2,4-dimethyl-2-(p-toluenesulfonyl)pentan-3-one.

[0092] The above glyoxime photoacid generators include bis-o-(p-toluenesulfonyl)-α-dimethylglyoxime, bis-o-(p-toluenesulfonyl)-α-dimethylglyoxime, bis-o-(p-toluenesulfonyl)-α-disithrohexylglyoxime, bis-o-(p-toluenesulfonyl)-2,3-pentanedioneglyoxime, bis-o-(p-toluenesulfonyl)-2-methyl-3,4-pentanedioneglyoxime, bis-o-(n-butanesulfonyl)-α-dimethylglyoxime, bis-o-(n-butanesulfonyl)-α-dimethylglyoxime, bis-o-(n-butanesulfonyl)-α-dimethylglyoxime, Bis-o-(n-butanesulfonyl)-2,3-pentanedioneglyoxime, bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedioneglyoxime, bis-o-(methanesulfonyl)-α-dimethylglyoxime, bis-o-(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis-o-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis-o-(tert-butanesulfonyl)-α-dimethylglyoxime, bis-o-(perfluorooctanesulfonyl)-α-dimethylglyoxime, bis-o-(cyclohexylsulfonyl)-α-dimethylglyoxime, bis-o-(benzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-fluorobenzenesulfonyl)-α-dimethylglyoxime, These include bis-o-(p-tert-butylbenzenesulfonyl)-α-dimethylglyoxime, bis-o-(xylenesulfonyl)-α-dimethylglyoxime, and bis-o-(cambosulfonyl)-α-dimethylglyoxime.

[0093] In one embodiment of the present invention, the photosensitive resin composition may further include an additive. Specifically, the additive may further include one or more of a surfactant, an antioxidant, a crosslinking agent, and a solvent.

[0094] In one embodiment of the present invention, the photosensitive resin composition may include all of the additives, including a surfactant, an antioxidant, a crosslinking agent, and a solvent.

[0095] In one embodiment of the present invention, the surfactant is a silicone-based surfactant or a fluorine-based surfactant, and specifically, the silicone-based surfactant is BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341v344, BYK-345v346, BYK-348, BYK-354, BYK-355, BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, BYK-390, etc. can be used, and as fluorinated surfactants, DIC (DaiNippon Ink & Chemicals) F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F-445, F-446, F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F-484, F-486, F-487, F-172D, MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130, TF-1116SF, TF-1131, TF1132, TF1027SF, TF-1441, TF-1442, etc. can be used, but are not limited to these.

[0096] In one embodiment of the present invention, the antioxidant may play a role in improving the elongation characteristics of the film after curing following reliability evaluation or its adhesion to metal materials. Furthermore, the antioxidant may suppress oxidative deterioration of the aliphatic groups or phenolic hydroxyl groups of the polyimide resin, and may suppress metal oxidation by exerting a rust-preventive effect on the metal material. Specific examples of the antioxidant include, but are not limited to, the following compounds.

[0097] In one embodiment of the present invention, the crosslinking agent is not particularly limited, and any agent applicable to the technical field can be used without limitation. The crosslinking agent may mainly be a thermal crosslinking agent or a radical monomer. Examples of the crosslinking agent include, but are not limited to, a compound having at least two alkoxymethyl groups and / or methylol groups, and a compound having at least two epoxy groups and / or oxetanyl groups. By including the above-mentioned compounds, a crosslinked structure can be formed by causing a condensation reaction with the resin of the present invention during firing after patterning, and the mechanical properties such as elongation of the cured resin pattern can be improved. In addition, two or more types of the crosslinking agent can be used in combination, thereby enabling various designs.

[0098] In one embodiment of the present invention, preferred examples of the compound having at least two alkoxymethyl groups and / or methylol groups include, for example, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DMLMBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOMBPE, TMOM-BPA, Examples include TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade names, manufactured by Honshu Kagaku Kogyo Co., Ltd.), NIKALAC (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (trade names, manufactured by Sanwa Chemical Co., Ltd.), and can be obtained from each company. Two or more of these may be contained.

[0099] In addition, preferred examples of compounds having at least two epoxy groups and / or oxetanyl groups include, but are not limited to, epoxy group-containing silicones such as bisphenol A type epoxy resin, bisphenol A type oxetanyl resin, bisphenol F type epoxy resin, bisphenol F type oxetanyl resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polymethyl(glycidyloxypropyl)siloxane. Specifically, EPICLON (registered trademark) 850-S, EPICLON HP-4032, EPICLON HP-7200, EPICLON HP-820, EPICLON HP-4700, EPICLON EXA-4710, EPICLON HP-4770, EPICLON EXA-859CRP, EPICLON EXA-1514, EPICLON EXA-4880, EPICLON EXA-4850-150, EPICLON EXA-4850-1000, EPICLON EXA-4816, EPICLON EXA-4822 (all product names, manufactured by Dainippon Ink & Chemicals Co., Ltd.), Ricarejin (registered trademark) BEO-60E (product name, Shin Nippon Examples include EP-4003S, EP-4000S (product name: manufactured by ADEKA Co., Ltd.), etc., and can be obtained from each company. Two or more of these may be included.

[0100] In addition, the crosslinking agent may be 2-[[4-[2-[4-[1,1-bis[4-(oxiran-2-ylmethoxy)phenyl]ethyl]phenyl]propan-2-yl]phenoxy]methyl]oxirane, Tetraethylene glycol dimethyacrylate, etc.

[0101] The content of the crosslinking agent is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, or even more preferably 10 parts by weight or more, based on 100 parts by weight of the total polyimide resin, and from the viewpoint of maintaining mechanical properties such as elongation, it is preferably 300 parts by weight or less, or more preferably 200 parts by weight or less.

[0102] In one embodiment of the present invention, in order to improve the resolution of the relief pattern, the photosensitive resin composition may additionally include a monomer having a photopolymerizable unsaturated bond. As such monomers, (meth)acrylic compounds that undergo radical polymerization by a photopolymerization initiator are preferable, and in particular, but not limited to, mono- or diacrylates and methacrylates of ethylene glycol or polyethylene glycol, including diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, mono- or diacrylates and methacrylates of propylene glycol or polypropylene glycol, mono-, di- or triacrylates and methacrylates of glycerol, cyclohexanediacrylate and dimethacrylate, diacrylates and dimethacrylates of 1,4-butanediol, diacrylates and dimethacrylates of 1,6-hexanediol, diacrylates and dimethacrylates of neopentyl glycol, mono- or diacrylates and methacrylates of bisphenol A, benzene trimethacrylate, isobornyl acrylate, and Examples of compounds include methacrylates, acrylamide and derivatives thereof, methacrylamide and derivatives thereof, trimethylolpropanetriacrylate and methacrylate, di- or triacrylates and methacrylates of glycerol, di-, tri-, or tetraacrylates and methacrylates of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds.

[0103] The content of the monomer having the above-mentioned photopolymerizable unsaturated bond is preferably 1 to 50 parts by weight based on 100 parts by weight of the total polyimide resin.

[0104] In one embodiment of the present invention, the solvent may be any compound known in the technical field to which the present invention pertains to enable the formation of a photosensitive resin composition, without particular limitation. As a non-limiting example, the solvent may be one or more compounds selected from the group consisting of esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides.

[0105] The above ester solvents are ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, gamma-butyrolactone, epsilon-caprolactone, delta-valerolactone, alkyl oxyacetic acids (e.g., methyl oxyacetic acid, ethyl oxyacetic acid, butyl oxyacetic acid (e.g., methyl methoxyacetic acid, ethyl methoxyacetic acid, butyl methoxyacetic acid, methyl ethoxyacetic acid, ethyl ethoxyacetic acid, etc.)), alkyl 3-oxypropionic acid esters (e.g., methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (e.g., 3-methoxypropionate methyl, 3-methoxypropionate ethyl, 3-ethoxypropionate methyl, 3-ethoxypropionate ethyl, etc.), 2-oxypropionic acid alkyl esters (e.g., 2-oxypropionate methyl, 2-oxypropionate ethyl, 2-oxypropionate propyl, etc. (e.g., 2-methoxypropionate methyl, 2-methoxypropionate ethyl, 2-methoxypropionate propyl, 2-ethoxypropionate methyl, 2-ethoxypropionate ethyl)), 2-oxy-2-methylpropionate methyl and 2-oxy-2-methylpropionate ethyl (e.g., 2-methoxy-2-methylpropionate methyl, 2-ethoxy-2-methylpropionate ethyl, etc.), methyl pyruvate, It can be ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc.

[0106] The above ether solvent may be diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc.

[0107] The above ketone solvent may be methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc.

[0108] The above aromatic hydrocarbon solvent may be toluene, xylene, anisole, limonene, etc.

[0109] The above sulfoxide solvent may be dimethyl sulfoxide, etc.

[0110] In one embodiment of the present specification, the photosensitive resin composition has a light transmittance of 350 mJ / cm 2 It may have the following sensitivities:

[0111] In one embodiment of the present specification, the photosensitive resin composition has an emission intensity of about 350 mJ / cm 2 Below, about 340 mJ / cm 2 Below, about 330 mJ / cm 2 Below, about 320 mJ / cm 2 or less, or about 310 mJ / cm 2 It may have the following sensitivity. The lower limit of sensitivity is not particularly limited, but is approximately 350 mJ / cm. 2 If the value is below, it may be judged to have excellent physical properties (e.g., easy micropatterning) as a photosensitive material.

[0112] In one embodiment of the present specification, the photosensitive resin composition may include 1 to 40 parts by weight of the photoinitiator; 5 to 50 parts by weight of the crosslinking agent; and 0.05 to 5 parts by weight of the surfactant, based on 100 parts by weight of the polyimide resin.

[0113] In one embodiment of the present specification, the photosensitive resin composition may include 50 to 500 parts by weight of the solvent relative to 100 parts by weight of the polyimide resin.

[0114] When each of the above components is included in the photosensitive resin composition in the weight range described above, sensitivity and physical properties can be improved even with a small amount of photoacid generator, and substrate adhesion can be improved.

[0115] [Polyimide resin]

[0116] In one embodiment of the present invention, the polyimide resin may be a polyimide resin having a structure represented by the following chemical formula 1; or a structure represented by the following chemical formula 2.

[0117] [Chemical Formula 1]

[0118]

[0119] [Chemical Formula 2]

[0120]

[0121] In the above chemical formulas 1 and 2,

[0122] means a part that is bonded to another substituent or repeating unit,

[0123] L is a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -SO2-; -CO-; or -OCO-,

[0124] R1 and R2 are the same or different, and each independently represent hydrogen; or a substituted or unsubstituted alkyl group,

[0125] r1 and r2 are equal to or different from each other, and are each independently an integer from 0 to 3, and when r1 is 2 or more, R1 is equal to or different from each other, and when r2 is 2 or more, R2 is equal to or different from each other,

[0126] Ra and Rb are the same or different from each other, and each independently represents hydrogen; or a structure represented by the following chemical formula a,

[0127] [chemical formula a]

[0128]

[0129] In the above chemical formula a,

[0130] means a part connected to the above chemical formula 1 or 2,

[0131] R3 is hydrogen; or a substituted or unsubstituted alkyl group,

[0132] q is an integer from 1 to 10.

[0133] A polyimide resin according to one embodiment of the present invention includes a flexible chain, a protection group having an alkali-insoluble property for an acid, and has the advantages of being able to be melted under high temperature conditions, thereby improving elongation, having hydrophilicity, and having excellent substrate adhesion. A photosensitive resin composition including the polyimide resin uses a photoacid generator (PAG) in a smaller amount than a photosensitive resin composition using a photoinitiator (PI) generally used in the art, so that it is easy to implement a fine pattern and has excellent resolution. In addition, the photosensitive resin composition according to the present specification can provide a large amount of a photosensitive resin composition having excellent sensitivity even when using a small amount of a photoacid generator.

[0134] Specifically, the polyimide resin according to one embodiment of the present invention has hydrophilicity by including a flexible chain containing an ester or ether group, and is imparted with melting property at a high temperature (about 100°C to 200°C), thereby improving substrate adhesion. In addition, since flexibility is imparted to the polyimide resin by the flexible chain, elongation is improved, thereby suppressing warping of the wafer. In addition, the glass transition temperature (Tg) of the polyimide resin is lowered, which helps in the diffusion of the photoacid generator included in the negative photosensitive resin composition, thereby improving resolution.

[0135] In this specification, may mean a portion that is bonded to another substituent or bonding moiety, and may mean a portion that is bonded to the main chain of the polymer of the present specification.

[0136] As used herein, "polymer" means a compound composed of repeating units (basic units). The polymer may be expressed as a polymer or a compound composed of a polymer.

[0137] In this specification, examples of substituents are described below, but are not limited thereto.

[0138] The term "substituted or unsubstituted" as used herein means substituted with one or more substituents selected from the group consisting of deuterium; halogen; nitrile; nitro; hydroxy; -COOH; alkoxy; alkyl; cycloalkyl; alkenyl; cycloalkenyl; aryl; heteroaryl; and heterocyclic group containing one or more of N, O, S or P atoms, or has no substituents.

[0139] In this specification, examples of halogen groups include fluorine, chlorine, bromine, or iodine.

[0140] In the present specification, the alkoxy group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but may be 1 to 30, specifically 1 to 20, and more specifically 1 to 10.

[0141] In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 60. In one embodiment, the alkyl group has 1 to 30 carbon atoms. In another embodiment, the alkyl group has 1 to 20 carbon atoms. In another embodiment, the alkyl group has 1 to 10 carbon atoms. Specific examples of the alkyl group include, but are not limited to, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, and the like. In the present specification, the cycloalkyl group is not particularly limited, but is preferably 3 to 30 carbon atoms, and in particular, a cyclopentyl group and a cyclohexyl group are preferred, but are not limited to these.

[0142] In this specification, the description of the alkyl group described above applies to the alkylene group, except that the alkyl group is divalent.

[0143] In the present specification, the cycloalkyl group is not particularly limited, but is preferably one having 3 to 60 carbon atoms. In one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. In another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. In yet another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, examples thereof include, but are not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

[0144] In the present specification, the alkenyl group may be linear or branched, and the carbon number is not particularly limited, but is preferably 2 to 60. In one embodiment, the alkyl group has 2 to 30 carbon atoms. In another embodiment, the alkyl group has 2 to 20 carbon atoms. In yet another embodiment, the alkyl group has 2 to 10 carbon atoms. Specific examples of the alkenyl group include, but are not limited to, an alkenyl group substituted with an aryl group such as a stylbenyl group or a styrenyl group.

[0145] In the present specification, the cycloalkenyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. In one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. In another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. In yet another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Examples of the cycloalkenyl group include, but are not limited to, a cyclopentenyl group and a cyclohexenyl group.

[0146] In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. In one embodiment, the aryl group has 6 to 30 carbon atoms. In one embodiment, the aryl group has 6 to 20 carbon atoms. The monocyclic aryl group may be, but is not limited to, a phenyl group, a biphenyl group, a terphenyl group, etc. The polycyclic aryl group may be, but is not limited to, a naphthyl group, an anthracenyl group, an indenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a triphenyl group, a chrysenyl group, a fluorenyl group, etc.

[0147] In this specification, the description of the aryl group described above applies to the arylene group, except that the aryl group is divalent.

[0148] In the present specification, the heterocyclic group is a heterocyclic group containing O, N or S as a heteroatom, and the number of carbon atoms is not particularly limited, but is 2 to 30 carbon atoms, specifically 2 to 20 carbon atoms. Examples of the heterocyclic group include, but are not limited to, a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a triazine group, an acridyl group, a pyridazine group, a quinolinyl group, an isoquinoline group, an indole group, a carbazole group, a benzoxazole group, a benzimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a dibenzofuran group, a tetrahydropyran, and the like. Preferably, the heterocyclic group is tetrahydropyran.

[0149] In this specification, the description of the heterocyclic group described above may be applied, except that the heteroaryl group is aromatic.

[0150] In the present specification, the aromatic ring may be an aryl group or a heteroaryl group, and the above-described description may be applied to the aryl group or heteroaryl group. The aliphatic ring may refer to a ring other than the aromatic ring.

[0151] In one embodiment of the present invention, L may be a direct bond; a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms; a substituted or unsubstituted arylene group having 6 to 30 carbon atoms; -SO2-; -CO-; or -OCO-.

[0152] In one embodiment of the present invention, L may be a direct bond; a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted arylene group having 6 to 20 carbon atoms; -SO2-; -CO-; or -OCO-.

[0153] In one embodiment of the present invention, L may be a direct bond; a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; a substituted or unsubstituted arylene group having 6 to 12 carbon atoms; -SO2-; -CO-; or -OCO-.

[0154] In one embodiment of the present invention, R1 and R2 are the same as or different from each other, and each independently may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0155] In one embodiment of the present invention, R1 and R2 are the same as or different from each other, and each independently may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0156] In one embodiment of the present invention, R1 and R2 are the same as or different from each other, and each independently may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0157] In one embodiment of the present invention, Ra and Rb are the same as or different from each other, and each independently represent hydrogen; or a structure represented by the following chemical formula a.

[0158] [chemical formula a]

[0159]

[0160] In one embodiment of the present invention, the chemical formula a may be any one of the structures below, and it is sufficient if q satisfies an integer from 1 to 10, and is not limited to the examples below.

[0161]

[0162] In one embodiment of the present invention, R3 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0163] In one embodiment of the present invention, R3 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0164] In one embodiment of the present invention, R3 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0165] In one embodiment of the present invention, at least one of Ra and Rb includes a structure represented by the chemical formula a, and the content of the structure represented by the chemical formula a may be greater than 0 mol% and less than or equal to 100 mol% relative to the total content of the polyimide resin.

[0166] In one embodiment of the present invention, at least one of Ra and Rb includes a structure represented by the chemical formula a, and the content of the structure represented by the chemical formula a may be 10 mol% or more and 100 mol% or less, 20 mol% or more and 100 mol% or less, 30 mol% or more and 100 mol% or less, 40 mol% or more and 100 mol% or less, 50 mol% or more and 100 mol% or less, 60 mol% or more and 100 mol% or less, 70 mol% or more and 100 mol% or less, 80 mol% or more and 100 mol% or less, 90 mol% or more and 100 mol% or less, or 100% relative to the total content of the polyimide resin.

[0167] In one embodiment of the present invention, the content of the structure represented by the chemical formula a relative to the total content of the polyimide resin can be confirmed by commercially available NMR, and after the completion of the resin synthesis reaction, the amount of OH before the reaction is derived from the number of protons of the total aromatic rings of the polyimide, and the content (mol%) of the structure represented by the chemical formula a can be confirmed through the number of protons of the chemical formula a (Integration of the peak of 6.41 to 5.83 ppm (3H)) relative to the amount of OH before the reaction.

[0168] In one embodiment of the present invention, the chemical formula 1 or 2 may be represented by any one of the following structural formulas.

[0169]

[0170]

[0171]

[0172] In the above structural formula, Ra and Rb are as defined in the above chemical formulas 1 and 2,

[0173] may refer to a moiety that is bonded to another substituent or repeating unit.

[0174] In one embodiment of the present invention, the polyimide resin may further include a structure represented by the following chemical formula E.

[0175] [Chemical Formula E]

[0176]

[0177] In the above chemical formula E,

[0178] means a part that is bonded to another substituent or repeating unit,

[0179] Re1 is hydrogen; or a substituted or unsubstituted alkyl group,

[0180] re1 is an integer from 0 to 4, and if re1 is 2 or greater, 2 or more Re1 are equal to or different from each other,

[0181] Re is hydrogen; or a structure represented by the above chemical formula a.

[0182] In one embodiment of the present invention, the structure represented by the chemical formula E may be an end group of the polyimide resin.

[0183] In one embodiment of the present invention, Re1 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0184] In one embodiment of the present invention, Re1 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0185] In one embodiment of the present invention, Re1 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0186] In one embodiment of the present invention, Re1 may be hydrogen; or a structure represented by the chemical formula a.

[0187] In one embodiment of the present invention, Re is a structure represented by the chemical formula a. The contents of the chemical formula a are as described above.

[0188] In one embodiment of the present invention, the polyimide resin may further include any one of the structures represented by any one of the following chemical formulas 3-1 to 3-4.

[0189] [Chemical Formula 3-1]

[0190]

[0191] [Chemical Formula 3-2]

[0192]

[0193] [Chemical Formula 3-3]

[0194]

[0195] [Chemical Formula 3-4]

[0196]

[0197] In the above chemical formulas 3-1 to 3-4,

[0198] means a part that is bonded to another substituent or repeating unit,

[0199] L1 to L3 are the same or different from each other, and each independently represents a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -CO-; -S-; -COO-L'-OCO-; -O-(L")mO-,

[0200] The above L' and L" are the same or different, and each independently represents a substituted or unsubstituted alkylene group; or a substituted or unsubstituted arylene group,

[0201] m is an integer from 1 to 5, and if m is 2 or greater, L" are equal to or different from each other,

[0202] Ra1 to Ra4 are the same or different from each other, and each independently represents hydrogen; or a substituted or unsubstituted alkyl group,

[0203] ra1 to ra4 are equal to or different from each other, and are each independently an integer from 0 to 3. When ra1 is 2 or more, Ra1 is equal to or different from each other, when ra2 is 2 or more, Ra2 is equal to or different from each other, when ra3 is 2 or more, Ra3 is equal to or different from each other, and when ra4 is 2 or more, Ra4 is equal to or different from each other.

[0204] Cy represents a substituted or unsubstituted aliphatic ring or aromatic ring.

[0205] In one embodiment of the present invention, any one of the chemical formulas 3-1 to 3-4 can be derived from any one of the following chemical formulas.

[0206]

[0207]

[0208]

[0209]

[0210]

[0211] In one embodiment of the present invention, the weight average molecular weight of the polyimide resin may be 3,000 g / mol to 70,000 g / mol. Specifically, the weight average molecular weight of the polyimide resin may be 5,000 g / mol to 50,000 g / mol. When the weight average molecular weight of the polyimide resin is less than 3,000 g / mol, the produced insulating film may be easily damaged or the adhesive strength may be reduced. In addition, when the weight average molecular weight of the polyimide resin exceeds 70,000 g / mol, the sensitivity may be reduced, development may not occur, or residues (e.g., scum) may remain, which is not preferable.

[0212] [Insulating film]

[0213] One embodiment of the present specification provides an insulating film comprising the photosensitive resin composition described above or a cured product thereof.

[0214] The above insulating film may contain the photosensitive resin composition as is.

[0215] The above insulating film may include a cured product of the photosensitive resin composition.

[0216] As a light source for curing the photosensitive resin composition according to one embodiment of the present invention, there may be, for example, a mercury vapor arc, a carbon arc, a Xe arc, etc. that emit light having a wavelength of 250 nm to 450 nm, but the present invention is not necessarily limited thereto.

[0217] After the above insulating film has been cured of the photosensitive resin composition, a step of heat treatment may be further performed, if necessary.

[0218] The above heat treatment can be performed by a heating means such as a hot plate, a hot air circulator, or an infrared furnace, and can be performed at a temperature of 180°C to 250°C, or 190°C to 220°C.

[0219] The above insulating film exhibits excellent chemical resistance and mechanical properties, and thus can be suitably applied to insulating films of semiconductor devices, interlayer insulating films for redistribution layers, etc. In addition, the insulating film can be applied to photoresists, etching resists, solder top resists, etc.

[0220] The above insulating film may include a support or a substrate.

[0221] The support or substrate is not particularly limited, and any known material in the art can be used. For example, a substrate for electronic components or a substrate having a predetermined wiring pattern formed thereon can be exemplified. Examples of the substrate include a metal substrate made of silicon, silicon nitride, titanium, tantalum, palladium, titanium tungsten, copper, chromium, iron, aluminum, gold, nickel, etc., or a glass substrate. Examples of the material for the wiring pattern can be copper, solder, chromium, aluminum, nickel, gold, etc., but is not limited thereto. Preferably, the support or substrate can be a silicon wafer.

[0222] The above coating method is not particularly limited, but may include spraying, roll coating, and spin coating, with spin coating being the most widely used method. Furthermore, after forming the coating film, some residual solvent may be removed under reduced pressure, depending on the case.

[0223] In one embodiment of the present invention, the thickness of the insulating film may be 1 μm to 100 μm. When the thickness range of the insulating film is satisfied, an insulating film having excellent chemical resistance and mechanical properties as desired in the present specification can be obtained. The thickness of the insulating film may be measured using a scanning electron microscope (SEM).

[0224] In one embodiment of the present invention, the insulating film including the photosensitive resin composition may have a good product ratio of 99% or more. The good product ratio of the insulating film refers to the ratio of the number of insulating films evaluated as good products to the total number of insulating films manufactured. The good product may refer to an insulating film in which a thermal cycle test (TC test) that applies thermal shock to the insulating film is performed, and the resistance values ​​before and after the TC test are measured, and the increase rate of the resistance value after the TC test to the resistance value before the TC test is less than 50%. That is, the insulating film including the photosensitive resin composition may have a good product ratio of 99% or more according to the following equation 2 after the TC test on the insulating film.

[0225] [Formula 2]

[0226] Good product ratio (%) = (Np1 / Nt1) X 100

[0227] In the above equation 2,

[0228] The above Np1 is the number of insulating films evaluated as good,

[0229] The above Nt1 is the total number of insulating films manufactured.

[0230] Here, the 'insulating film' refers to an evaluation substrate including an insulating film formed on a substrate having copper wiring formed thereon, and may refer to a substrate including an insulating film manufactured from the same photosensitive resin composition as the 'film sample' manufactured for the aforementioned physical property evaluation. In addition, the conditions for forming the insulating film included in the evaluation substrate may be the same as the conditions for forming the film sample described above, except for development and pattern formation.

[0231] For example, the above-mentioned 'evaluation substrate' may mean a substrate formed by forming a copper wire on a silicon wafer, applying the photosensitive resin composition on the copper wire, exposing and curing it, and then developing it to form an insulating film pattern having a thickness of 5 to 10 μm. It may also be manufactured by applying flux on the insulating film pattern, forming solder balls, and connecting them to electrodes.

[0232] Here, the TC test may refer to a thermal cycle test (TC test) that applies thermal shock by repeating one cycle 700 times for 30 minutes each under low temperature (-55 ℃) and high temperature (125 ℃) conditions.

[0233] An insulating film according to one embodiment of the present invention includes the photosensitive resin composition having high elongation, low sensitivity, and excellent adhesion to a substrate, and therefore, warpage of a wafer in a semiconductor device using the insulating film can be suppressed and reliability can be excellent.

[0234] [Semiconductor devices]

[0235] One embodiment of the present invention provides a semiconductor device including the insulating film.

[0236] The above semiconductor device may be manufactured by including various components commonly used in the relevant technical field in addition to the above insulating film.

[0237] In one embodiment of the present invention, the semiconductor device including the insulating film may have a good yield rate of 99% or more. The good yield rate of the semiconductor device refers to the ratio of the number of semiconductor devices evaluated as 'good' to the total number of semiconductor devices manufactured. The 'good' may refer to a semiconductor device in which a thermal cycle test (TC test) that applies thermal shock to a 'semiconductor device' is performed, and the resistance values ​​before and after the TC test are measured, and the increase rate of the resistance value after the TC test to the resistance value before the TC test is less than 50%. That is, the semiconductor device including the insulating film may have a good yield rate of 99% or more according to the following equation 3 after the TC test on the 'semiconductor device'.

[0238] [Formula 3]

[0239] Good product ratio (%) = (Np2 / Nt2) X 100

[0240] In the above equation 3,

[0241] The above Np2 is the number of semiconductor devices evaluated as good,

[0242] The above Nt2 is the total number of semiconductor devices manufactured.

[0243] Here, the 'semiconductor device' refers to a semiconductor device including an insulating film formed on a substrate on which copper wiring is formed, and may refer to a semiconductor device including an insulating film manufactured from the same photosensitive resin composition as the 'film sample' manufactured for the above-described property evaluation, and the conditions for forming the insulating film included in the semiconductor device may be the same as the conditions for forming the film sample described above, except for development and pattern formation.

[0244] Additionally, the thermal cycle test (TC test) performed on the semiconductor device may be performed under the same conditions as the TC test performed on the insulating film described above.

[0245] A semiconductor device according to one embodiment of the present invention includes the photosensitive resin composition having high elongation, low sensitivity, and excellent adhesion to a substrate, so that warpage of a wafer in a semiconductor device using the insulating film can be suppressed and reliability can be excellent.

[0246] Hereinafter, the present invention will be described in detail using examples. However, the examples according to the present invention may be modified in various ways, and the scope of the present invention is not limited to the examples described below. The examples in this specification are provided to more fully explain the present invention to those of ordinary skill in the art.

[0247] Polymerization example

[0248] Polymerization Example 1

[0249] 2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane (1eq), polyetheramine (D-400, Jeffamine) (0.25eq), 4,4'-oxydiphthalic anhydride (1.35eq), and 3-aminophenol (0.16eq) were dissolved in PGMEA (Propylene glycol methyl ether acetate) under a N2 atmosphere. Toluene was added to the reaction mixture at 150°C, Dean-Stark was connected, and the reaction was carried out overnight at 180°C. After the reaction, the toluene in Dean-Stark was removed, and PGMEA was substituted several times to remove the residual toluene. The polymer 1-1 having the following structural formula was manufactured by confirming the residual monomer by NMR and terminating the reaction. When the molecular weight of the polymer 1-1 was measured using gel permeation chromatography (GPC), the weight average molecular weight was confirmed to be 17,000 g / mol.

[0250] Polymer 1-1

[0251]

[0252] In the above polymer 1-1, n, o and p are values ​​such that the weight average molecular weight of the polymer has a value of 17,000 g / mol, n is an integer from 2 to 15, o is an integer from 5 to 40, and p is an integer from 2 to 15.

[0253] Polymerization Example 2

[0254] 2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane (1eq), 4,4'-oxydiphthalic anhydride (1.1eq), and 3-aminophenol (0.13eq) were dissolved in PGMEA under a N2 atmosphere. Toluene was added to the reaction mixture at 150°C, Dean-Stark was connected, and the reaction was carried out overnight at 180°C. After the reaction, the toluene of Dean-Stark was removed, and then PGMEA was substituted several times to remove the residual toluene. The reaction was terminated by confirming the residual monomer by NMR, and polymer 1-2 was prepared. When the molecular weight of the polymer 1-2 was measured using gel permeation chromatography (GPC), the weight average molecular weight was confirmed to be 18,000 g / mol.

[0255] Polymer 1-2

[0256]

[0257] In the above polymer 1-2, o is a value having a weight average molecular weight of the polymer of 18,000 g / mol, and o is an integer from 5 to 40.

[0258] Polymerization Example 3

[0259] 2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane (0.6 eq), polyetheramine (ED-2003, Jeffamine) (0.4 eq), 4,4'-oxydiphthalic anhydride (1.1 eq), and 3-aminophenol (0.13 eq) were dissolved in PGMEA under a N2 atmosphere. Toluene was added to the reaction mixture at 150°C, Dean-Stark was connected, and the reaction was carried out overnight at 180°C. After the reaction, the toluene in Dean-Stark was removed, and PGMEA was substituted several times to remove the residual toluene. The polymer 1-3 was manufactured by confirming the residual monomer by NMR and terminating the reaction. When the molecular weight of the polymer 1-3 was measured using gel permeation chromatography (GPC), the weight average molecular weight was confirmed to be 23,000 g / mol.

[0260] Polymer 1-3

[0261]

[0262] Synthetic example

[0263] Synthesis Example 1

[0264] In the polymer 1-1 manufactured in the above polymerization example 1, 0.1 eq of triethylamine, 0.32 eq of 2-Isocyanatoethyl acrylate and PGMEA were additionally added in proportion to the OH of polyimide, and stirred at 80°C. Then, 5.64 ppm (2H) of 2-Isocyanatoethyl acrylate disappeared by NMR, and a new peak was confirmed at 3.15 ppm (2H), and the reaction was terminated. The total OH number in the polymer was derived from the total aromatic ring area on NMR, and using the average values ​​of 6.41 (1H), 6.12 (1H), and 5.83 (1H), the hydrogen of the R group below had a structure corresponding to chemical formula a (i.e., ) was confirmed. It was confirmed that a total of 30 mol% was substituted. When the molecular weight was measured using gel permeation chromatography (GPC), the weight average molecular weight was 21,000 g / mol. The structure of polymer 2-1 according to the above synthesis example 1 is as follows.

[0265] Polymer 2-1

[0266]

[0267] In the above polymer 2-1, n, o and p are values ​​such that the weight average molecular weight of the polymer has a value of 21,000 g / mol, n is an integer from 2 to 15, o is an integer from 5 to 40, and p is an integer from 2 to 15.

[0268] Synthesis Example 2

[0269] Polymer 2-2 was synthesized in the same manner as in Synthesis Example 1, except that polymer 1-2 of the above-mentioned polymerization example 2 was used instead of polymer 1. The hydrogen of the R group below has a structure corresponding to chemical formula a (i.e., ) was confirmed to be a total of 30 mol%. When the molecular weight of the polymer 2-2 was measured using gel permeation chromatography (GPC), the weight average molecular weight was confirmed to be 22,000 g / mol. The structure of the polymer 2-2 according to the above synthesis example 2 is as follows.

[0270] Polymer 2-2

[0271]

[0272] In the above polymer 2-2, o is a value having a weight average molecular weight of the polymer of 22,000 g / mol, and o is an integer from 5 to 40.

[0273] Synthesis Example 3

[0274] Polymer 2-3 was synthesized in the same manner as in Synthesis Example 1, except that polymer 1-3 of the above-mentioned polymerization example 3 was used instead of polymer 1. The hydrogen of the R group below has a structure corresponding to chemical formula a (i.e., ) was confirmed to be a total of 30 mol%. When the molecular weight of the polymer 2-3 was measured using gel permeation chromatography (GPC), the weight average molecular weight was confirmed to be 24,000 g / mol. The structure of the polymer 2-3 according to the above synthesis example 3 is as follows.

[0275] Polymer 2-3

[0276]

[0277] Examples and Comparative Examples

[0278] Manufacturing Example 1 - Manufacturing of a photosensitive resin composition

[0279] A photosensitive resin composition was prepared using the components described in Table 1 below. Specifically, based on 100 parts by weight of the prepared polyimide resin, a photosensitive resin composition was prepared by including 200 parts by weight of a solvent (PGMEA) and the weight part of each component described in Table 1 below.

[0280] Polyimide resin photoinitiator crosslinking agent surfactant type weight part type weight part type weight part type weight part Manufacturing example 1-1 Polymer 2-1100B10C20E0.1 Manufacturing example 1-2 Polymer 2-1100B10D20E0.1 Manufacturing example 1-3 Polymer 2-1100B10D40E0.1 Manufacturing example 1-4 Polymer 2-2100B10C20E0.1 Manufacturing example 1-5 Polymer 2-2100B10D20E0.1 Manufacturing example 1-6 Polymer 2-2100B10D40E0.1 Manufacturing example 1-7 Polymer 2-3100B10C20E0.1

[0281] In Table 1 above, B to E mean the following.

[0282] B: OXE-01 (BASF Company)

[0283] C: Poly(ethylene glycol) (200) diacrylate (Miramer M282, Miwon Company)

[0284] D: Poly(ethylene glycol) (200) diacrylate (Miramer M286, Miwon Company)

[0285] E: BYK-331 (BYK-Chemie company)

[0286] Manufacturing Example 2 - Manufacturing of Film

[0287] The photosensitive resin compositions of Manufacturing Examples 1-1 to 1-7 were each cured under the following conditions to produce films of Manufacturing Examples 2-1 to 2-7 having a thickness of 10 μm. Specifically, the produced photosensitive resin compositions were applied onto a substrate by spin coating. Then, a soft bake (SOB) was performed, and after exposure at an appropriate exposure dose (sensitivity) using an exposure device, a post bake (PB) was performed. At this time, the film production conditions are as follows.

[0288] SOB 105℃ / 120s, PB 200℃ / 1hr, thickness 10㎛

[0289] Exposure: 200 mJ / ㎠ to 900 mJ / ㎠ i-line stepper

[0290] Experimental Example - Measurement and Evaluation of Film Properties

[0291] The physical properties of the films obtained in Manufacturing Examples 2-1 to 2-7 were measured by the following methods, and the results are shown in Table 2.

[0292] Experimental Example 1 - Coefficient of Thermal Expansion (CTE)

[0293] The above film was prepared in a size of 5 mm x 20 mm, and then the sample was loaded using an accessory. The thickness and length of the film sample to be actually measured were the same at 10 μm and 16 mm, respectively. The pulling force of the film sample was set to 0.01 N, and the first temperature increasing process was performed at a temperature increasing rate of 10 °C / min in the temperature range of 50 °C to 100 °C, and then the thermal expansion change pattern when cooling at a cooling rate of 10 °C / min in the temperature range of 50 °C to 100 °C was measured using a TMA (TA Q400), and is shown in Table 2 below.

[0294] Experimental Example 2 - Elongation at break, tensile strength, and Young's modulus

[0295] After producing film samples with a size of 10 mm × 100 mm and a thickness of 10 ㎛ for the films manufactured in Manufacturing Examples 2-1 to 2-7, the elongation at break (%), tensile strength (MPa), and Young's modulus (GPa) of each film sample were measured at room temperature and a speed of 5 mm / min using a UTM (Universal Testing Machine), and are shown in Table 2 below.

[0296] Experimental Example 3 - Deriving Temperature Cycle Evaluation Factors

[0297] Based on the coefficient of thermal expansion, Young's modulus, tensile strength and elongation at break of the film samples measured in Experimental Examples 1 and 2 above, the temperature cycle evaluation factor (I) according to Equation 1 below TC ) was calculated, and the evaluation results are shown in Table 2 below.

[0298] [Formula 1]

[0299] I TC = [(Y 2 ×T×E) / (CC Cu )]

[0300] (Y: Young's modulus of the film / (GPa), T: Tensile strength of the film / (Mpa), E: Elongation at break of the film / (%), C: Coefficient of thermal expansion of the film / (ppm / ℃), C Cu: Coefficient of thermal expansion of copper / (ppm / ℃))

[0301] Experimental Example 4 - Reliability Evaluation (TC Test)

[0302] The photosensitive resin compositions obtained in Manufacturing Examples 1-1 to 1-7 were prepared.

[0303] A copper wire was formed on a silicon wafer, and the photosensitive resin compositions of Manufacturing Examples 1-1 to 1-7 were applied, exposed, cured, and then developed on the copper wire to form an insulating film pattern having a thickness of 10 μm. Thereafter, flux was applied and solder balls were formed on the insulating film pattern, and connected to electrodes to prepare evaluation substrates each including the photosensitive resin compositions obtained in Manufacturing Examples 1-1 to 1-7. At this time, the conditions for forming the insulating film pattern are as follows.

[0304] SOB 105℃ / 120s, PB 200℃ / 1hr, thickness 10㎛

[0305] Exposure: 200 mJ / ㎠ to 900 mJ / ㎠ i-line stepper

[0306] Develope: 23℃, 2.38 wt% TMAH (Tetramethylammonium hydroxide) solution, Dipping, DI water rinse

[0307] For the above evaluation substrate, a thermal cycle test (TC test) was performed in which thermal shock was applied by repeating 700 cycles of 30 minutes each at low temperature (-55°C) and high temperature (125°C) conditions to evaluate the reliability of the evaluation substrate, i.e., the insulating film including the photosensitive resin composition.

[0308] Specifically, if the good product ratio of the insulating film according to Equation 2 below is 99% or more after the TC test for the insulating film, the insulating film was evaluated as a good product.

[0309] [Formula 2]

[0310] Good product ratio (%) = (Np1 / Nt1) X 100

[0311] In the above equation 2,

[0312] The above Np1 is the number of insulating films evaluated as good,

[0313] The above Nt1 is the total number of insulating films manufactured.

[0314] Afterwards, if the quality ratio of the insulating film according to the above formula 2 after the above TC test is 99% or more, it is evaluated as '○', and if it is less than 99%, it is evaluated as 'Х', and this is shown in Table 2 below.

[0315] Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Film Manufacturing Example 2-1 Manufacturing Example 2-2 Manufacturing Example 2-3 Manufacturing Example 2-4 Manufacturing Example 2-5 Manufacturing Example 2-6 Manufacturing Example 2-7 Photosensitive resin composition Manufacturing Example 1-1 Manufacturing Example 1-2 Manufacturing Example 1-3 Manufacturing Example 1-4 Manufacturing Example 1-5 Manufacturing Example 1-6 Manufacturing Example 1-7 Curing conditions (℃ / 1 hr) 200 200 200 200 200 200 C / (ppm / ℃) 445 160 495 660 62 C Cu / (ppm / ℃)17171717171717Young's modulus / (GPa)3.42.92.72.92.72.11.7Tensile strength / (Mpa)131125120160120135120Elongation at break / (%)616575607070100Evaluation factor(I TC )34212010152625231570969771TC test○○○○○ХХ

[0316] Referring to Table 1, the films according to Examples 1 to 5 have excellent heat resistance properties with a coefficient of thermal expansion (C, CTE) value of 60 ppm / ℃ or less, and satisfy the properties required for semiconductor insulating films such as elongation at break, tensile strength, and Young's modulus, while also having a temperature cycle evaluation factor (I TC) value is 1000 or more, and the ratio of good products after the thermal cycle test (TC test) is 99% or more, confirming that the reliability of the manufactured insulating film is excellent. On the other hand, the temperature cycle evaluation factor (I TC ) The films according to Comparative Examples 1 and 2, in which the value is less than 1000, had a ratio of good products of less than 99% after the thermal cycle test, confirming that the reliability of the manufactured insulating film was inferior.

[0317] That is, the photosensitive resin composition according to Examples 1 to 5 of the present invention can form an insulating film having excellent elongation, sensitivity, and / or adhesion to a substrate, and it was confirmed that the insulating film including the photosensitive resin composition also has excellent reliability as a result of a TC test. Through this, it can be seen that the photosensitive resin composition according to one embodiment of the present invention can provide a photosensitive resin composition capable of forming a highly reliable insulating film in a simpler manner through measuring a predetermined physical property of a film sample and calculating an evaluation factor.

[0318] Furthermore, since the insulating film and semiconductor device according to one embodiment of the present invention include the photosensitive resin composition having high elongation, low sensitivity, and excellent adhesion to a substrate, it can be seen that warping of a wafer in a semiconductor device using the insulating film can be suppressed and reliability is excellent.

[0319] The detailed description above exemplifies and explains the present invention. Furthermore, the foregoing merely illustrates and describes preferred embodiments of the present invention. As described above, the present invention can be used in various other combinations, modifications, and environments, and changes or modifications can be made within the scope of the inventive concept disclosed herein, the scope equivalent to the above-described disclosure, and / or the scope of technology or knowledge in the art. Therefore, the detailed description of the invention above is not intended to limit the present invention to the disclosed embodiments. Furthermore, the appended claims should be construed to include other embodiments.

Claims

1. A photosensitive resin composition comprising a polyimide resin, The above photosensitive resin composition is cured to produce a film having a thickness of 10 ㎛, When the coefficient of thermal expansion, Young's modulus, tensile strength and elongation at break of the above film were measured, I according to the following equation 1 TC A photosensitive resin composition having a value of 1000 or more: [Formula 1] I TC = [(Y 2 ×T×E) / (C-C Cu )] In the above equation 1, Above I TC is the temperature cycle evaluation factor of the above film, The above Y is the Young's modulus of the film, The above T is the tensile strength of the film, The above E is the breaking elongation of the film, The above C is the coefficient of thermal expansion of the film, C above Cu is the coefficient of thermal expansion of copper.

2. In paragraph 1, A photosensitive resin composition wherein the above curing is performed under temperature conditions of 160°C or higher and 240°C or lower.

3. In paragraph 1, A photosensitive resin composition having a thermal expansion coefficient measured using a thermal expansion coefficient measuring device at a temperature of 50°C or higher and 100°C or lower.

4. In paragraph 1, The above polyimide resin is, A structure represented by the following chemical formula 1; or A photosensitive resin composition comprising a polyimide resin having a structure represented by the following chemical formula 2: [Chemical Formula 1] [Chemical Formula 2] In the above chemical formulas 1 and 2, means a part that is bonded to another substituent or repeating unit, L is a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -SO2-; -CO-; or -OCO-, R1 and R2 are the same or different, and each independently represent hydrogen; or a substituted or unsubstituted alkyl group, r1 and r2 are equal to or different from each other, and are each independently an integer from 0 to 3, and when r1 is 2 or more, R1 is equal to or different from each other, and when r2 is 2 or more, R2 is equal to or different from each other, Ra and Rb are the same or different from each other, and each independently represents hydrogen; or a structure represented by the following chemical formula a, [chemical formula a] In the above chemical formula a, means a part connected to the above chemical formula 1 or 2, R3 is hydrogen; or a substituted or unsubstituted alkyl group, q is an integer from 1 to 10.

5. In paragraph 4, A photosensitive resin composition wherein the polyimide resin further comprises a structure represented by the following chemical formula E as a terminal group: [Chemical Formula E] In the above chemical formula E, means a part that is bonded to another substituent or repeating unit, Re1 is hydrogen; or a substituted or unsubstituted alkyl group, re1 is an integer from 0 to 4, and if re1 is 2 or greater, 2 or more Re1 are equal to or different from each other, Re is hydrogen; or a structure represented by the above chemical formula a.

6. In paragraph 4, The above polyimide resin is, A photosensitive resin composition further comprising any one of the structures represented by any one of the following chemical formulas 3-1 to 3-4: [Chemical Formula 3-1] [Chemical Formula 3-2] [Chemical Formula 3-3] [Chemical Formula 3-4] In the above chemical formulas 3-1 to 3-4, means a part that is bonded to another substituent or repeating unit, L1 to L3 are the same or different and each independently a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -CO-; -S-; -COO-L'-OCO-; or -O-(L")mO-, The above L' and L" are the same or different, and each independently represents a substituted or unsubstituted alkylene group; or a substituted or unsubstituted arylene group, m is an integer from 1 to 5, and if m is 2 or greater, L" are equal to or different from each other, Ra1 to Ra4 are the same or different from each other, and each independently represents hydrogen; or a substituted or unsubstituted alkyl group, ra1 to ra4 are equal to or different from each other, and are each independently an integer from 0 to 3. When ra1 is 2 or more, Ra1 is equal to or different from each other, when ra2 is 2 or more, Ra2 is equal to or different from each other, when ra3 is 2 or more, Ra3 is equal to or different from each other, and when ra4 is 2 or more, Ra4 is equal to or different from each other. Cy represents a substituted or unsubstituted aliphatic ring or aromatic ring.

7. In paragraph 1, Contains more additives, A photosensitive resin composition wherein the additive further comprises at least one of a surfactant, an antioxidant, a crosslinking agent, and a solvent.

8. An insulating film comprising a photosensitive resin composition according to any one of claims 1 to 7 or a cured product thereof.

9. A semiconductor device including an insulating film according to Article 8.

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