Photosensitive resin composition, insulating film and semiconductor device

Abstract

The present invention relates to a photosensitive resin composition, which is soluble in an environmentally friendly aqueous solvent, can be developed with an aqueous developer, and can provide an insulating film that has excellent chemical resistance, low dielectric constant characteristics, low dielectric loss characteristics, and mechanical properties.

Description

[Technical Field]

[0001] This application is a national phase application of International Application No. PCT / KR2024 / 006000, filed on May 3, 2024. The present invention relates to a photosensitive resin composition, an insulating film, and a semiconductor device. This application claims the benefit of the filing date of Korean Patent Application No. 10-2023-0061852, filed with the Korean Intellectual Property Office on May 12, 2023, the entire contents of which are incorporated herein by reference. [Background technology]

[0002] Polyimide-based resins and polybenzoxazole-based resins, which have excellent heat resistance and mechanical properties, have been widely used for surface protective films and interlayer insulating films of semiconductor elements in electronic devices. When forming thin films containing these resins, a high-temperature heat treatment at around 350°C is usually required to thermally dehydrate and ring-close a coating of a polyimide precursor or polybenzoxazole precursor to obtain a thin film with excellent heat resistance and mechanical properties.

[0003] However, in recent years, due to demands for reducing the thermal load on devices and reducing warpage, there has been a demand for polyimide-based resins or polybenzoxazole-based resins that can be cured by heat treatment at low temperatures of approximately 250°C or less, more preferably 200°C or less. Summary of the Invention [Problem to be solved by the invention]

[0004] The technical problem to be solved by the present invention is to provide a photosensitive resin composition that can be dissolved in an environmentally friendly aqueous solvent, can be developed with an aqueous developer, and can provide an insulating film that has excellent chemical resistance, low dielectric constant characteristics, low dielectric loss characteristics, and mechanical properties. However, the problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description. [Means for solving the problem]

[0005] One embodiment of the present invention provides a photosensitive resin composition comprising a polyimide having repeating units represented by the following Chemical Formulas 1 to 4, wherein the ratio of the total number of -F functional groups to the total number of -OH functional groups contained in the repeating units represented by the Chemical Formulas 1 to 4 satisfies 2≦-F / -OH≦5:

[0006] [ka]

[0007] In the above formulas 1 to 4, A1 is a tetravalent aliphatic organic group, A2 is a tetravalent aromatic ring group, B1 is a divalent aromatic ring group, B2 is a flexible functional group, p1 to p4 are each independently an integer of 1 to 10,000, and at least one of A1, A2, B1, and B2 contains a -F, -OH, or -F and -OH functional group.

[0008] Another embodiment of the present application provides an insulating film comprising the photosensitive resin composition or a cured product thereof. Another embodiment of the present application provides a semiconductor device including the insulating film. [Effects of the Invention]

[0009] A photosensitive resin composition according to one embodiment of the present invention includes a polyimide containing repeating units represented by Chemical Formulas 1 to 4, and the ratio between the total number of -F functional groups and the total number of -OH functional groups contained in the repeating units represented by Chemical Formulas 1 to 4 satisfies 2≦-F / -OH≦5. This has the advantages of being easily soluble in environmentally friendly aqueous solvents such as propylene glycol monomethyl ether acetate (PGMEA) and being developable in aqueous developers such as TMAH (tetramethylammonium hydroxide).

[0010] Specifically, in order for the photosensitive resin composition to be easily dissolved in PGMEA, an environmentally friendly aqueous solvent, and to be developable in TMAH, an aqueous developer, -F and -OH functional groups are required. However, the more -F and -OH functional groups there are, the greater the dielectric loss D f However, there are disadvantages such as poor physical properties such as elongation and poor chemical resistance.

[0011] However, a photosensitive resin composition according to one embodiment of the present invention includes a polyimide having repeating units represented by Chemical Formulas 1 to 4, and the ratio between the total number of -F functional groups and the total number of -OH functional groups contained in the repeating units represented by Chemical Formulas 1 to 4 satisfies 2≦-F / -OH≦5. This has the advantages of being easily soluble in PGMEA, an environmentally friendly aqueous solvent, and being developable using TMAH, an aqueous developer, and can provide an insulating film having low dielectric constant characteristics, low dielectric loss characteristics, and excellent mechanical properties such as elongation, as well as chemical resistance.

[0012] The effects of the present invention are not limited to those described above, and effects not mentioned herein will be clearly understood by those skilled in the art from the present specification and the accompanying drawings. DETAILED DESCRIPTION OF THE INVENTION

[0013] In this specification, when a part is said to "comprise" a certain element, this means that it can further include other elements, but not to the exclusion of other elements, unless otherwise specified to the contrary. Throughout this specification, when a member is said to be "on" another member, this does not only include when the member is in contact with the other member, but also when there is another member between the two members. Throughout this specification, the unit "parts by weight" can refer to the weight ratio between each component.

[0014] In this specification, terms including ordinal numbers, such as "first" and "second," are used to distinguish one component from another, and are not limited by the ordinal number. For example, within the scope of the present invention, a first component can also be named a second component, and similarly, a second component can be named a first component. Throughout this specification, the unit "molar parts" can refer to the molar ratio between each component. Throughout this specification, "(meth)acrylate" is used in the colloquial sense to refer to acrylate and methacrylate.

[0015] As used herein, the term "polymer" refers to a compound consisting of a repeating unit (basic unit). The polymer may be expressed as a polymer or a compound consisting of a polymer.

[0016] Throughout this specification, the "weight-average molecular weight" and "water-average molecular weight" of a compound can be calculated using the molecular weight and molecular weight distribution of that compound. Specifically, a sample containing 1 wt% of the compound is prepared by placing tetrahydrofuran (THF) and the compound in a 1 ml glass vial. The standard (polystyrene) and the sample are filtered through a filter (pore size 0.45 μm) and then injected into a GPC injector. The elution time of the sample is compared with the calibration curve of the standard sample to obtain the molecular weight and molecular weight distribution of the compound. An Infinity II 1260 (Agilient) can be used as the measuring instrument, with a flow rate of 1.00 mL / min and a column temperature of 40.0°C.

[0017] Throughout this specification, the term "substituted" means that another functional group is bonded in place of a hydrogen atom in a compound, and the position of the substitution is not limited as long as it is a position where a hydrogen atom is substituted, i.e., a position where a substituent can be substituted, and when two or more substituents are substituted, the two or more substituents may be the same or different from each other.

[0018] As used herein, the term "substituted or unsubstituted" refers to a group substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, halogen, cyano, nitro, hydroxy, carbonyl, ester, imide, amide, primary amino, carboxy, sulfonic acid, sulfonamide, phosphine oxide, alkoxy, aryloxy, alkylthioxy, arylthioxy, alkylsulfoxy, arylsulfoxy, silyl, boron, alkyl, cycloalkyl, alkenyl, aryl, aralkyl, aralkenyl, alkylaryl, alkoxysilylalkyl, arylphosphine, or heterocyclic groups containing one or more N, O, and S atoms, or a group substituted or unsubstituted with two or more of the above-exemplified substituents linked together. For example, a "substituent linked to two or more substituents" may be a biphenyl group. That is, a biphenyl group may be an aryl group or may be interpreted as a substituent linked to two phenyl groups.

[0019] Throughout this specification, an "aliphatic cyclic group" or an "aromatic cyclic group" may be understood to mean a single ring existing by itself, or two or more rings joined together to form a fused ring, or two or more rings linked by a direct bond, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O)2-, -OCO-, -Si(CH3)2-, or a substituted or unsubstituted alkylene group.

[0020] Throughout this specification: [ka] indicates the moiety where the group is connected to another adjacent atom.

[0021] Throughout this specification, "-F" refers to a fluorine functionality contained in a compound, and "-OH" refers to a hydroxy functionality contained in a compound. Throughout this specification, the ratio between the number of -F functional groups and the number of -OH functional groups contained in a polymer or a repeating unit, -F / -OH, means the value calculated by dividing the total number of moles of -F functional groups contained in the monomers used in the polymerization of the polymer or repeating unit by the total number of moles of -OH functional groups.

[0022] The present invention will be described in more detail below. [Photosensitive resin composition] One embodiment of the present invention provides a photosensitive resin composition comprising a polyimide having repeating units represented by the following Chemical Formulas 1 to 4, wherein the ratio of the total number of -F functional groups to the total number of -OH functional groups contained in the repeating units represented by the Chemical Formulas 1 to 4 satisfies 2≦-F / -OH≦5:

[0023] [ka]

[0024] In the above formulas 1 to 4, A1 is a tetravalent aliphatic organic group, A2 is a tetravalent aromatic ring group, B1 is a divalent aromatic ring group, B2 is a flexible functional group, p1 to p4 are each independently an integer of 1 to 10,000, and at least one of A1, A2, B1, and B2 contains a -F, -OH, or -F and -OH functional group.

[0025] Generally, the polyimide contained in the photosensitive resin composition must contain -F and -OH functional groups in order to be easily soluble in PGMEA, an environmentally friendly aqueous solvent, and developable in TMAH, an aqueous developer.

[0026] However, if the polyimide is easily soluble in PGMEA, an environmentally friendly aqueous solvent, and contains a large number of -F and -OH functional groups to enable development in TMAH, an aqueous developer, the dielectric loss D f However, there are disadvantages such as poor physical properties such as elongation and poor chemical resistance.

[0027] The -F functional group has advantages in terms of solubility and low dielectric loss characteristics, but if it is present in an excessive amount, it may actually increase dielectric loss and reduce the physical properties of the film.The -OH functional group has advantages in terms of development and solubility, but because it is highly hygroscopic, if its content is high, it may have adverse effects on reliability, etc.

[0028] The photosensitive resin composition according to one embodiment of the present invention has the advantage that the ratio between the total number of -F functional groups and the total number of -OH functional groups contained in the repeating units represented by the chemical formulas 1 to 4 satisfies 2≦-F / -OH≦5, and is therefore easily soluble in PGMEA, an environmentally friendly aqueous solvent, and can be developed in TMAH, an aqueous developer. f and dielectric constant D k It is possible to provide a photosensitive resin composition having low viscosity, excellent mechanical properties such as elongation, and excellent chemical resistance.

[0029] According to one embodiment of the present invention, the polyimide may include terminal groups derived from an end-capping compound, as described below.

[0030] According to one embodiment of the present invention, the photosensitive resin composition may be a positive type photosensitive resin composition or a negative type photosensitive resin composition.

[0031] According to one embodiment of the present invention, the weight-average molecular weight of the polyimide may be 1,000 g / mol to 70,000 g / mol. More preferably, the weight-average molecular weight of the polyimide may be 5,000 g / mol to 50,000 g / mol, 10,000 g / mol to 70,000 g / mol, 10,000 g / mol to 50,000 g / mol, 15,000 g / mol to 50,000 g / mol, 15,000 g / mol to 40,000 g / mol, or 20,000 g / mol to 40,000 g / mol. If the weight-average molecular weight of the polyimide resin is less than 1,000 g / mol, the resulting insulating film may become brittle and adhesive strength may decrease. Furthermore, if the weight-average molecular weight of the polyimide resin exceeds 70,000 g / mol, sensitivity may decrease, resulting in undeveloped or scum residue.

[0032] The -F / -OH ratio is preferably 2.1 or more, more preferably 2.5 or more, and even more preferably 3.0 or more. The -F / -OH ratio is preferably 4.8 or less, more preferably 4.5 or less or 4.3 or less, and even more preferably 4.0 or less.

[0033] If the ratio of -F / -OH is less than 2, the dielectric loss value increases and chemical resistance decreases, and the relatively high ratio of -OH functional groups increases moisture absorption, resulting in reduced reliability.

[0034] On the other hand, if the ratio of -F / -OH exceeds 5, the dielectric loss value increases, and the mechanical properties and chemical resistance of the film decrease.

[0035] The repeating unit represented by Chemical Formula 1 includes A1, an aliphatic moiety derived from an aliphatic dianhydride monomer, and B1, an aromatic moiety derived from a diamine monomer containing no flexible functional group; the repeating unit represented by Chemical Formula 2 includes A2, an aromatic moiety derived from an aromatic dianhydride monomer, and B1, an aromatic moiety derived from a diamine monomer containing no flexible functional group; the repeating unit represented by Chemical Formula 3 includes A1, an aliphatic moiety derived from an aliphatic dianhydride monomer, and B2, a flexible moiety derived from a diamine monomer containing a flexible functional group; and the repeating unit represented by Chemical Formula 4 includes A2, an aromatic moiety derived from an aromatic dianhydride monomer, and B2, a flexible moiety derived from a diamine monomer containing a flexible functional group.

[0036] A typical photosensitive resin composition contains a polymer of an aromatic dianhydride monomer and a diamine monomer that does not contain a flexible functional group. However, a photosensitive resin composition according to an embodiment of the present invention uses an aliphatic dianhydride monomer having an aliphatic moiety introduced therein to reduce dielectric loss, and a diamine monomer that contains a flexible functional group to improve elongation.

[0037] However, the aliphatic moiety contained in the polyimide for reducing the dielectric loss value and the flexible moiety contained in the polyimide for improving elongation must be contained in an appropriate amount because if the amount is outside the appropriate content range, the physical properties of the photosensitive resin composition may deteriorate.

[0038] Specifically, the photosensitive resin composition according to one embodiment of the present invention has the advantages of being easily soluble in PGMEA, an environmentally friendly aqueous solvent, and being developable in TMAH, an aqueous developer. In addition, to provide a photosensitive resin composition that has excellent physical properties such as dielectric loss and elongation, and excellent chemical resistance, the polyimide containing repeating units represented by Chemical Formulas 1 to 4 contains an aliphatic moiety and a flexible moiety in an appropriate content.

[0039] According to one embodiment of the present invention, the ratio of the total number of repeating units represented by Chemical Formulas 1 and 3 to the total number of repeating units represented by Chemical Formulas 2 and 4 may be 0.01 to 1.0.

[0040] When the ratio of the total number of repeating units represented by Chemical Formulae 1 and 3 to the total number of repeating units represented by Chemical Formulae 2 and 4 satisfies 0.01 to 1.0, the content of aliphatic moieties contained in the polyimide is appropriate, and therefore the photosensitive resin composition is easily soluble in PGMEA, an environmentally friendly aqueous solvent, and can be developed using TMAH, an aqueous developer, and has low dielectric loss D f It can have a value.

[0041] More specifically, the ratio of the total number of repeating units represented by the chemical formulae 1 and 3 to the total number of repeating units represented by the chemical formulae 2 and 4 is preferably 0.01 or more, more preferably 0.05 or more, and even more preferably 0.1 or more. Furthermore, the ratio of the total number of repeating units represented by the chemical formulae 1 and 3 to the total number of repeating units represented by the chemical formulae 2 and 4 is preferably 1.0 or less, more preferably 0.9 or less or 0.8 or less, and even more preferably 0.7 or less.

[0042] If the ratio of the total number of repeating units represented by Chemical Formulae 1 and 3 to the total number of repeating units represented by Chemical Formulae 2 and 4 is less than 0.01, the compound may be difficult to dissolve in PGMEA, an environmentally friendly aqueous solvent, or may have poor developability in TMAH, an aqueous developer. If the ratio exceeds 1.0, the dielectric loss properties may be poor.

[0043] According to one embodiment of the present invention, the ratio of the total number of repeating units represented by Chemical Formulae 1 and 3 to the total number of repeating units represented by Chemical Formulae 1 to 4 may be 0.05 to 0.5. By satisfying this ratio, a photosensitive resin composition can be obtained that is easily soluble in PGMEA, an environmentally friendly aqueous solvent, developable in TMAH, an aqueous developer, and has a low dielectric loss value.

[0044] If the ratio of the total number of repeating units represented by Chemical Formulae 1 and 3 to the total number of repeating units represented by Chemical Formulae 1 to 4 is less than 0.05, the compound may be difficult to dissolve in PGMEA, an environmentally friendly aqueous solvent, or may have poor developability in TMAH, an aqueous developer. If the ratio exceeds 0.5, the dielectric loss properties may be poor.

[0045] According to one embodiment of the present invention, the ratio of the total number of repeating units represented by Chemical Formulae 3 and 4 to the total number of repeating units represented by Chemical Formulae 1 to 4 may be 0.05 to 0.5.

[0046] When the ratio of the total number of repeating units represented by Chemical Formulae 3 and 4 to the total number of repeating units represented by Chemical Formulae 1 to 4 satisfies 0.05 to 0.5, the content of flexible moieties contained in the polyimide is appropriate, and therefore, a photosensitive resin composition can be obtained that is easily soluble in PGMEA, an environmentally friendly aqueous solvent, and developable in TMAH, an aqueous developer, and also has excellent adhesion, elongation, and chemical resistance.

[0047] If the ratio of the total number of repeating units represented by Chemical Formulae 3 and 4 to the total number of repeating units represented by Chemical Formulae 1 to 4 is less than 0.05, the compound may be difficult to dissolve in PGMEA, an environmentally friendly aqueous solvent, and problems such as reduced developability and reduced adhesion in TMAH, an aqueous developer, may occur. If the ratio exceeds 0.5, the compound may have reduced elongation and chemical resistance.

[0048] According to one embodiment of the present invention, the tetravalent aliphatic organic group (A1) may include one or more substituted or unsubstituted tetravalent aliphatic cyclic groups selected from the group consisting of the following Chemical Formula 5 and the following Chemical Formula 6:

[0049] [ka]

[0050] In the above chemical formulas 5 and 6, L1 is a direct bond, a substituted or unsubstituted alkylene group, -O-, -SO2-, -CO-, or -OCO-; R1 to R6 are the same or different and each independently represent hydrogen, a substituted or unsubstituted alkyl group, or a carboxy group; m and n are 2; R5 are the same or different; and R6 are the same or different. More specifically, the tetravalent aliphatic organic group (A1) may include one or more groups selected from the following chemical formulae:

[0051] [ka]

[0052] According to one embodiment of the present invention, the tetravalent aromatic ring group (A2) may include one or more selected from a substituted or unsubstituted tetravalent aromatic monocyclic ring and the following formula 7:

[0053] [ka]

[0054] In the above Chemical Formula 7, L2 is a direct bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, -O-, -SO2-, -CO-, or -OCO-; R1 and R2 are the same or different and each independently represent hydrogen, a substituted or unsubstituted alkyl group, or a carboxy group; m and n are the same or different and each independently represent an integer of 0 to 3; when m is 2 or greater, R1 are the same or different; and when m is 2 or greater, R2 are the same or different.

[0055] According to one embodiment of the present invention, the divalent aromatic ring group (B1) may include one or more selected from a substituted or unsubstituted divalent aromatic monocyclic ring, the following Chemical Formula 8, and the following Chemical Formula 9:

[0056] [ka]

[0057] In the above Chemical Formulas 8 and 9, L3 and L4 are the same or different and each independently represent a direct bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, -O-, -SO2-, -CO-, or -OCO-; R1 to R4 are the same or different and each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a hydroxyl group, or a substituted or unsubstituted amine group; m1, m2, n1, and n2 are the same or different and each independently represent an integer of 0 to 4; when m1 is 2 or greater, R1 are the same or different; when n1 is 2 or greater, R2 are the same or different; when m2 is 2 or greater, R3 are the same or different; and when n2 is 2 or greater, R4 are the same or different.

[0058] According to one embodiment of the present invention, the flexible functional group (B2) may include one or more selected from the following formulas 10 to 13.

[0059] [ka]

[0060] In the above Chemical Formulas 10 to 13, X1 to X3 are the same or different and each independently represent -O- or -CH2-; La1 to La11 are the same or different and each independently represent a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group; R1 to R6 are the same or different and each independently represent hydrogen or a substituted or unsubstituted alkyl group; x, y, and z are each independently a real number from 0 to 50; and a1 is a real number from 1 to 30.

[0061] More specifically, the flexible functional group (B2) may include one or more selected from the following chemical formulae:

[0062] [ka]

[0063] In the above formula, n is independently a real number from 1 to 30, and x, y, and z are independently a real number from 1 to 50.

[0064] [Monomers for polyimide synthesis] In the polyimide containing the repeating units represented by Chemical Formulas 1 to 4, each repeating unit may be obtained by reacting a dianhydride with a diamine. More specifically, the dianhydride may be a tetracarboxylic dianhydride.

[0065] Specifically, the repeating unit represented by Chemical Formula 1 may be obtained by reacting an aliphatic dianhydride monomer with a diamine monomer not containing a flexible functional group, the repeating unit represented by Chemical Formula 2 may be obtained by reacting an aromatic dianhydride monomer with a diamine monomer not containing a flexible functional group, the repeating unit represented by Chemical Formula 3 may be obtained by reacting an aliphatic dianhydride monomer with a diamine monomer containing a flexible functional group, and the repeating unit represented by Chemical Formula 4 may be obtained by reacting an aromatic dianhydride monomer with a diamine monomer containing a flexible functional group.

[0066] Aliphatic Dianhydride Monomer According to one embodiment of the present invention, the aliphatic dianhydride monomer may include one or more selected from the following formulas 14 to 16:

[0067] [ka]

[0068] In the above Chemical Formulas 14 to 16, Cy1 is a substituted or unsubstituted aliphatic monocycle, L1 is a direct bond, a substituted or unsubstituted alkylene group, -O-, -SO2-, -CO-, or -OCO-, Ra to Rd are the same or different and each independently represent hydrogen, a substituted or unsubstituted alkyl group, or a carboxy group, m and n are the same or different and each independently represent an integer of 0 to 3, and when m is 2 or more, Ra are the same or different, and when n is 2 or more, Rb are the same or different.

[0069] More specifically, the aliphatic dianhydride monomer may include one or more selected from the following chemical formulas:

[0070] [ka]

[0071] According to an embodiment of the present invention, the aliphatic dianhydride monomer may include an aliphatic dianhydride monomer having a substituted or unsubstituted alkyl group and an aliphatic dianhydride monomer having a substituted or unsubstituted aliphatic ring. When the aliphatic dianhydride monomer includes all of the above monomers, a photosensitive resin composition including a polyimide polymerized therefrom has the advantages of being easily soluble in PGMEA, an environmentally friendly aqueous solvent, and being developable in TMAH, an aqueous developer. At the same time, the dielectric loss D f The film has excellent physical properties and may also have excellent chemical resistance.

[0072] Aromatic Dianhydride Monomer According to one embodiment of the present invention, the aromatic dianhydride monomer may include at least one selected from the following formulas 17 and 18:

[0073] [ka]

[0074] In the above Chemical Formula 17, Cy2 is a substituted or unsubstituted aromatic ring group; and in the above Chemical Formula 18, L2 is a direct bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, -O-, -SO2-, -CO-, or -OCO-; Ra and Rb are the same or different and each independently represent hydrogen, a substituted or unsubstituted alkyl group, or a carboxy group; m and n are the same or different and each independently represent an integer of 0 to 3; when m is 2 or more, Ra are the same or different; and when n is 2 or more, Rb are the same or different.

[0075] According to an embodiment of the present invention, the aromatic dianhydride monomer may include, but is not limited to, one or more selected from the following chemical formulas:

[0076] [ka]

[0077] Diamine monomers that do not contain flexible functional groups According to one embodiment of the present invention, the diamine monomer not containing a flexible functional group may include one or more selected from the following formulas 19 to 21:

[0078] [ka]

[0079] In the above Chemical Formulas 19 to 21, L3 and L4 are the same or different and each independently represent a direct bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, -O-, -SO2-, -CO-, or -OCO-; Ra to Re are the same or different and each independently represent hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a hydroxy group, or a substituted or unsubstituted amine group; m1, m2, m3, n2, and n3 are the same or different and each independently represent an integer of 0 to 4; when m1 is 2 or greater, Ra are the same or different; when m2 is 2 or greater, Rb are the same or different; when m3 is 2 or greater, Rd are the same or different; when n2 is 2 or greater, Rc are the same or different; and when n3 is 2 or greater, Re are the same or different.

[0080] Diamine monomers containing flexible functional groups According to an embodiment of the present invention, the diamine monomer having a flexible functional group may have an amine group bound to each end of the flexible functional group. Specifically, the flexible functional group may be any one selected from the flexible functional groups represented by Formulas 10 to 13, or two or more flexible functional groups bonded to each other, with amine groups bonded to both ends of the flexible functional groups.

[0081] End-capping Compounds According to one embodiment of the present invention, the polyimide polymerized from the dianhydride monomer and the diamine monomer may be end-capped with an end-capping compound. According to one embodiment of the present invention, the end-capping compound may be a monoamine compound containing one amine group, a monoanhydride compound, or a mixture thereof.

[0082] For example, the end-capping compound may be trimellitic anhydride, phthalic anhydride, 5-Norbornene-2,3-dicarboxylic anhydride, 3-aminophenol (3AP is 3-aminophenol), or a mixture thereof.

[0083] [Additives] According to an embodiment of the present invention, the photosensitive resin composition may further include one or more selected from the group consisting of a photosensitizer, a crosslinker, an antioxidant, a surfactant, and a solvent. The photosensitive resin composition may also include additives known in the art depending on its intended use.

[0084] The photosensitizer may include a photoacid generator or a combination of a photopolymerization initiator and a compound having two or more ethylenically unsaturated bonds. By including a photoacid generator, acid is generated in the irradiated areas, increasing the solubility of the irradiated areas in an alkaline aqueous solution, thereby obtaining a positive-type relief pattern in which the irradiated areas are dissolved. Furthermore, by including a photoacid generator and an epoxy compound or a crosslinking agent, the acid generated in the irradiated areas promotes the crosslinking reaction of the epoxy compound or crosslinking agent, thereby obtaining a negative-type relief pattern in which the irradiated areas are insolubilized. Furthermore, by including a photopolymerization initiator and a compound having two or more ethylenically unsaturated bonds, active radicals generated in the irradiated areas promote radical polymerization of the ethylenically unsaturated bonds, thereby obtaining a negative-type relief pattern in which the irradiated areas are insolubilized.

[0085] Examples of the photoacid generator include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts.

[0086] Examples of the quinone diazide compound include a polyhydroxy compound to which a sulfonic acid of quinone diazide is bonded via an ester bond, a polyamino compound to which a sulfonic acid of quinone diazide is bonded via a sulfonamide bond, and a polyhydroxypolyamino compound to which a sulfonic acid of quinone diazide is bonded via an ester bond and / or a sulfonamide bond. These polyhydroxy compounds and polyamino compounds are preferably those in which 50 mol % or more of the functional groups are substituted with quinone diazide. Substitution of 50 mol % or more with quinone diazide improves the solubility of the resin film in an alkaline developer in the exposed areas, resulting in the advantageous effect of obtaining a fine pattern with high contrast with the unexposed areas. Furthermore, the composition preferably contains two or more photoacid generators, which allows for the production of a heat-resistant resin composition with high photosensitivity.

[0087] As the quinone diazide compound, either a compound having a 5-naphthoquinone diazide sulfonyl group or a compound having a 4-naphthoquinone diazide sulfonyl group is preferably used. 4-naphthoquinone diazide sulfonyl ester compounds have absorption in the i-line region of a mercury lamp and are suitable for i-line exposure. 5-naphthoquinone diazide sulfonyl ester compounds have absorption up to the g-line region of a mercury lamp and are suitable for g-line exposure. It is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength of exposure. Alternatively, a naphthoquinone diazide sulfonyl ester compound having both a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule may be included, or both a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound may be included.

[0088] Among the photoacid generators, sulfonium salts, phosphonium salts, and diazonium salts are preferred because they appropriately stabilize the acid component generated by exposure. Among these, sulfonium salts are preferred. If necessary, an acid increaser or decreaser may be further included.

[0089] Examples of the photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl-phenyl ketone, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 2-methyl-[4-(methylthio)phenyl]-2-morpholino 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, alkylated benzophenone, 3,3',4,4'-tetra(t-butyl)benzophenone Peroxycarbonyl)benzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethanaminium bromide, (4-benzoylbenzyl)trimethylammonium chloride, 2-hydroxy-3-(4-benzoylphenoxy)-N,N,N-trimethyl-1-propyleneaminium chloride monohydrate, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2-hydroxy- 3-(3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2,4,6-trimethylbenzoylphenylphosphine oxide, 1,2-octanedione-1-[4-(phenylthio)-2-(o-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime), 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2-Bimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzil, 9,10-phenanthrenequinone, camphorquinone, methylphenylglyoxyester, η5-cyclopentadienyl-η6-cumenyl-iron(1+)-hexafluorophosphate(1-), diphenyl sulfide derivatives, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 4 ,4-Bis(dimethylamino)benzophenone, 4,4-bis(diethylamino)benzophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 4-benzoyl-4-methylphenyl ketone, dibenzyl ketone, fluorenone, 2,3-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, benzyl methoxyethyl acetal, anthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberone, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis(p-azidobenzylidene)cyclohexane, 2,6-bis(p-azidobenzylidene)-4-methylcyclohexanone, 2-phenyl-1,2-butadione-2-(o-methoxycarbonyl)oxime, 1,3-diphenyl Examples include propanetrione-2-(o-ethoxycarbonyl)oxime, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile, benzthiazole disulfide, triphenylphosphine, carbon tetrabromide, tribromophenyl sulfone, benzoyl peroxide, and the like, or a combination of a photoreducible dye such as eosin or methylene blue with a reducing agent such as ascorbic acid or triethanolamine. Two or more of these may be used.

[0090] The content of the photosensitizer is preferably 0.05 to 50 parts by weight per 100 parts by weight of the polyimide. When the photosensitizer is a photoacid generator, the content is preferably 0.01 to 50 parts by weight per 100 parts by weight of the polyimide from the viewpoint of high sensitivity. The content of the quinone diazide compound among the photoacid generators is preferably 3 to 40 parts by weight. Furthermore, the total content of the sulfonium salt, phosphonium salt, and diazonium salt is preferably 0.5 to 20 parts by weight per 100 parts by weight of the polyimide. This content range is preferable because sufficient acid is generated upon irradiation with light, improving sensitivity. Furthermore, a content of the photoacid generator of 20 parts by weight or less is preferable because no residue is left in the developed pattern.

[0091] The content of the photopolymerization initiator is preferably 0.1 to 20 parts by weight relative to 100 parts by weight of the polyimide. If the content is 0.1 part by weight or more, sufficient radicals are generated by light irradiation, improving sensitivity. If the content is 20 parts by weight or less, excessive radicals are not generated, preventing curing of unexposed areas, improving alkaline developability. The content of the compound having two or more ethylenically unsaturated bonds is preferably 5 to 50 parts by weight relative to 100 parts by weight of the polyimide. If the content is 5 parts by weight or more, a cured resin film with high mechanical properties can be obtained by crosslinking, which is preferable. If the content is 50 parts by weight or less, sensitivity is not impaired, which is preferable.

[0092] The crosslinking agent is not particularly limited, and any crosslinking agent applicable to the technical field can be used without limitation. For example, the crosslinking agent can be a thermal crosslinking agent or a radical monomer. More specifically, the crosslinking agent can be, but is not limited to, a compound having at least two alkoxymethyl groups and / or methylol groups, or a compound having at least two epoxy groups and / or oxetanyl groups. By including these compounds, a condensation reaction with the polyimide resin occurs during baking after patterning to form a crosslinked structure, thereby improving the mechanical properties, such as the elongation of the cured resin pattern. Furthermore, two or more types of crosslinking agents can be used, thereby enabling a wider range of designs.

[0093] Preferred examples of the compound having at least two alkoxymethyl groups and / or methylol groups include DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, 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, T Examples of such compounds include ML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, and HMOM-TPHAP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), and NIKALAC (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, and NIKALAC MX-750LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.), which are available from various companies. Two or more of these compounds may be used.

[0094] Preferred examples of the compound having at least two epoxy groups and / or oxetanyl groups include, but are not limited to, bisphenol A epoxy resins, bisphenol A oxetanyl resins, bisphenol F epoxy resins, bisphenol F oxetanyl resins, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and epoxy group-containing silicones such as polymethyl(glycidyloxypropyl)siloxane. Specific examples include EPICLON® 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, and EPICLON EXA-485. Examples of such resins include EP-0-150, Epiclon EXA-4850-1000, Epiclon EXA-4816, and Epiclon EXA-4822 (all trade names, manufactured by Dainippon Ink and Chemicals, Inc.), Rikaresin (registered trademark) BEO-60E (trade name, manufactured by New Japan Chemical Co., Ltd.), and EP-4003S and EP-4000S (trade names, manufactured by ADEKA Corporation), which are available from various companies. Two or more of these may be used.

[0095] Furthermore, 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, or the like.

[0096] The content of the crosslinking agent is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and even more preferably 10 parts by weight or more, relative to 100 parts by weight of the polyimide, and from the viewpoint of maintaining mechanical properties such as elongation, is preferably 300 parts by weight or less, more preferably 200 parts by weight or less.

[0097] In one embodiment of the present invention, the photosensitive resin composition may further include a monomer having a photopolymerizable unsaturated bond in order to improve the resolution of the relief pattern.

[0098] Such a monomer is preferably a (meth)acrylic compound that undergoes a radical polymerization reaction in the presence of a photopolymerization initiator, and includes, but is not limited to, mono- or diacrylates and methacrylates of ethylene glycol or polyethylene glycol, such as 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, cyclohexane diacrylate and dimethacrylate, diacrylate and dimethacrylate of 1,4-butanediol, 1,6 -hexanediol diacrylate and dimethacrylate, neopentyl glycol diacrylate and dimethacrylate, bisphenol A mono- or diacrylate and methacrylate, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, glycerol di- or triacrylate and methacrylate, pentaerythritol di-, tri-, or tetraacrylate and methacrylate, and ethylene oxide or propylene oxide adducts of these compounds.

[0099] The content of the monomer having a photopolymerizable unsaturated bond is preferably 1 to 50 parts by weight based on 100 parts by weight of the polyimide.

[0100] The antioxidant can improve the elongation properties of the cured film after reliability evaluation and its adhesion to metal materials. The antioxidant can also inhibit oxidative degradation of aliphatic groups and phenolic hydroxyl groups in the polyimide resin, and inhibit metal oxidation through its rust-preventing effect on metal materials. Specific examples of the antioxidant include, but are not limited to, the following compounds:

[0101] [ka] [ka] [ka] [ka] [ka] [ka]

[0102] The content of the antioxidant is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, relative to 100 parts by weight of the polyimide. If the content of the antioxidant is less than 0.1 part by weight, it is difficult to obtain the effects of improving the elongation properties after reliability evaluation and the adhesion to metal materials, while if it exceeds 10 parts by weight, there is a risk of reducing the sensitivity of the photosensitive resin composition due to interaction with the photosensitizer.

[0103] The surfactant is a silicone surfactant or a fluorine surfactant. Specifically, the silicone 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, B YK-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. As the fluorine-based surfactant, DIC (DaiNippon Ink & 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 manufactured by (Finance Chemicals) , 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.

[0104] The solvent may be any compound known in the art to which the present invention pertains that can form a photosensitive resin composition, without any particular limitation. Non-limiting examples of the solvent include one or more compounds selected from the group consisting of esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides.

[0105] Examples of the ester solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, gamma-butyrolactone, epsilon-caprolactone, delta-valerolactone, alkyl oxyacetates (e.g., methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-oxypropionates (e.g., methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), and alkyl 3-oxypropionates (e.g., methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.). methyl 2-oxypropionate, ethyl 2-oxypropionate, etc.), alkyl 2-oxypropionates (e.g., methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc.

[0106] The ether solvent may be diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellulosolve acetate, ethyl cellulosolve 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, or the like.

[0107] The ketone solvent may be methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, or the like. The aromatic hydrocarbon solvent may be toluene, xylene, anisole, limonene, or the like. The sulfoxide solvent may be dimethyl sulfoxide or the like.

[0108] [Insulating film] Another embodiment of the present application provides an insulating film comprising the photosensitive resin composition or a cured product thereof. The insulating film may contain the photosensitive resin composition as it is. The insulating film may include a cured product of the photosensitive resin composition.

[0109] Examples of light sources for curing the photosensitive resin composition according to one embodiment of the present invention include, but are not limited to, mercury vapor arcs, carbon arcs, and Xe arcs that emit light having a wavelength of 250 nm to 450 nm.

[0110] After the photosensitive resin composition is cured, the insulating film may be subjected to a step of heat treatment, if necessary. The heat treatment may be carried out by a heating means such as a hot plate, a hot air circulator, or an infrared ray circulator, at a temperature of 180°C to 250°C, or 190°C to 220°C.

[0111] The insulating film exhibits excellent chemical resistance and mechanical properties and can be suitably used as an insulating film for semiconductor devices, an interlayer insulating film for rewiring layers, etc. The insulating film can also be used as a photoresist, an etching resist, a solder top resist, etc. The insulating film may include a support or a substrate.

[0112] The support or substrate is not particularly limited, and any known support or substrate in the art can be used. Examples include substrates for electronic components and substrates having a predetermined wiring pattern formed thereon. Examples of the substrate include metal substrates such as silicone, silicon nitride, titanium, tantalum, palladium, titanium tungsten, copper, chromium, iron, aluminum, gold, and nickel, and glass substrates. Materials for the wiring pattern may include, but are not limited to, copper, solder, chromium, aluminum, nickel, and gold. Preferably, the support or substrate may be a silicone wafer.

[0113] The coating method is not particularly limited, and may be a spray method, a roll coating method, a spin coating method, etc., and generally, a spin coating method is widely used. After forming the coating film, the residual solvent may be partially removed under reduced pressure, if necessary.

[0114] In one embodiment of the present invention, the insulating film may have a thickness of 1 μm to 100 μm. When the insulating film has a thickness within this range, an insulating film having excellent chemical resistance and mechanical properties, which is the objective of the present application, can be obtained. The thickness of the insulating film can be measured using a scanning electron microscope (SEM).

[0115] One embodiment of the present invention provides a semiconductor device including the insulating film. The semiconductor device may be manufactured by further including various components commonly used in the art in addition to the insulating film.

[0116] Hereinafter, the present invention will be described in detail with reference to examples. However, the examples of the present invention may be modified into various other forms, and the scope of the present invention should not be construed as being limited to the examples described below. The examples in this specification are provided to more completely explain the present invention to those skilled in the art.

[0117] Synthesis Examples 1 to 10 (Polyimide Resins A to J) and Comparative Synthesis Examples 1 to 7 (Polyimide Resins K to Q) A 1,000 mL round-bottom flask was used as a reaction vessel. The diamine monomer without flexible functional groups, the diamine monomer with flexible functional groups, and 300 g of the solvent PGMEA (propylene glycol methyl ether acetate) were sequentially added. The temperature was raised to 120 °C and stirred until completely dissolved. The flask was then cooled to 80 °C, and 30 g of the aromatic dianhydride monomer, the aliphatic dianhydride monomer, the end-capping monomer, and toluene were added and stirred at 150 °C. After completely dissolving the reactants, the flask was cooled to 50 °C. 3 mmol of gamma valerolactone (r-VL) and 7 mmol of triethylamine (TEA) diluted in 10 g of PGMEA were then added. The reaction vessel was equipped to remove water via a Dean-Stark distillation apparatus and stirred at 175 °C for 18 hours. After removing the toluene from the mixed solution, the solution was cooled to room temperature and the polymer was recovered, and the weight average molecular weight (Mw) of the recovered polymer was confirmed using gel permeation chromatography (GPC).

[0118] The types of monomers used in the synthesis of polyimide resins A to Q, the number of moles (mmol) of the monomers added, and the weight average molecular weights and polydispersity indexes (PDIs) of the recovered polymers are shown in Table 1 below.

[0119] [Table 1]

[0120] The abbreviations or detailed product names of the diamine monomers and dianhydride monomers shown in Table 1 above are as follows:

[0121] As diamine monomers that do not contain flexible functional groups, Bis-APAF is 2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane, BAPP is 2,2-Bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-ODA is 4,4'-Oxydianiline, HAB is 3,3'-Dihydroxy-4,4'-diaminobiphenyl, and p-PDA is p-Phenylenediamine.

[0122] As diamine monomers containing flexible functional groups, ED-2003, ED-900, ED-600 and D400 are Jeffamine® products, EC130 and EC280 are Baxxodur® products, and DAD is dodecane-1,12-diamine.

[0123] As the aromatic dianhydride monomer, ODPA is 4,4'-oxydiphthalic anhydride, 6FDA is 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, PMDA is pyromellitic dianhydride, and BPDA is 3,3',4,4'-biphenyltetracarboxylic dianhydride.

[0124] As aliphatic dianhydride monomers, CBDA is Cyclobutane-1,2,3,4-tetracarboxylic dianhydride, H-PMDA is 1,2,4,5-Cyclohexanetetracarboxylic dianhydride, H-BPDA is Dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, and BT-100 is 1,2,3,4-butane-tetracarboxylic dianhydride.

[0125] As end-capping compounds, TMA is trimelitic anhydride, 3AP is 3-aminophenol, PA is phthalic anhydride, and NDA is cis-5-Norbornene-endo-2,3-dicarboxylic anhydride.

[0126] Photosensitive resin composition The polyimide resins of the Synthesis Examples and Comparative Synthesis Examples prepared above, a curing agent, a photoactive compound, a surfactant, and a solvent were mixed in the compositions and amounts described below, and then stirred for 24 hours to prepare positive-type photosensitive resin compositions.

[0127] Example 1. Photosensitive resin composition A A positive photosensitive resin composition was prepared by mixing 23.8% of the polyimide resin A of Synthesis Example 1, 5.00% of EXA-4850-1000 (DIC Corporation) as a bisphenol A epoxy resin, 1.45% of YDF-170 (Kukdo Chemical Co., Ltd.) as a bisphenol F epoxy resin, 0.70% of HMMM (hexamethoxymethyl methylamine, TCI Corporation) as a methylol curing agent, 3.60% of TPD523 (Bigen Shosha Co., Ltd.) as a photosensitive material, 0.05% of R-40 (DIC Corporation) as a surfactant, 50.40% of PGMEA, and 15.00% of GBL (gamma butyrolactone) and stirring for 24 hours. Each value represents the weight percent of each component, based on 100% by weight of the resin composition.

[0128] Examples 2 to 10 and Comparative Examples 1 to 7 In Examples 2 to 10, photosensitive resin compositions were prepared in the same manner as in Example 1, except that polyimide resins B to J were used instead of the polyimide resin A. In Comparative Examples 1 to 7, photosensitive resin compositions were prepared in the same manner as in Example 1, except that polyimide resins K to Q were used instead of the polyimide resin A.

[0129] <Experimental Example> 1) Preparation of measurement samples The photosensitive resin composition prepared above was spin-coated onto a 6-inch wafer to form a film, which was then initially cured at 120°C for 2 minutes to evaporate the solvent. This was then finally cured in a nitrogen atmosphere in an oven (Koyo INH oven) at 180°C for 2 hours, resulting in a film thickness of 10 μm. To remove the cured film from the wafer, it was immersed in 2.5% HF diluted in DI-water (deionized water) for 30 minutes. Once the film floated up, it was removed and washed three times with DI-water. The resulting cured film was dried in a convection oven at 40°C for 1 hour and then cut into a 10 cm x 1 cm sample for tensile testing.

[0130] 2) Measurement of Young's modulus, tensile strength and elongation The prepared sample was loaded into a Universal Testing Machine (UTM, manufactured by Zwick) at 25°C, and the Young's modulus, tensile strength, and elongation were measured. The measurement length of the sample was 5 cm, and the pulling speed was set to 10.0 mm / min.

[0131] 3) Measurement of glass transition temperature (Tg) and coefficient of thermal expansion (CTE) Using a TA Q400 device, the prepared sample was heated at a rate of 10°C / min under a nitrogen atmosphere at a temperature of 25°C, and the glass transition temperature and the thermal expansion coefficient were measured.

[0132] 4) Optimal exposure (E op ) evaluation The photosensitive resin composition prepared above was spin-coated on a 6-inch wafer and then soft baked (pre-baked, SOB) at 120°C for 2 minutes. Then, it was exposed to light at 200mJ / cm 2 to 500mJ / cm 2The resist pattern was formed by exposure at 10 mJ intervals up to 2000 s, followed by development in a 2.38% aqueous solution of TMAH (Tetramethylammonium hydroxide) at 23°C for 120 seconds. op confirmed.

[0133] [Table 2]

[0134] In the case of Examples 1 to 10, which are photosensitive resin compositions according to the present invention in which the -F / -OH ratio contained in the polyimide repeating unit is 2 or more and 5 or less, there are advantages in that they are easily soluble in PGMEA, an environmentally friendly aqueous solvent, and can be developed using TMAH, an aqueous developer. In addition, they have excellent elongation and glass transition temperature.

[0135] On the other hand, in the case of Comparative Example 2, where the ratio of -F / -OH is 33, development using TMAH, an aqueous developer, is not possible, and in the cases of Comparative Examples 1 to 5, where the ratio of -F / -OH is more than 5, the elongation and glass transition temperature characteristics are inferior compared to the Examples. Comparative Examples 6 and 7, where the ratio of -F / -OH is less than 2, are inferior to the Examples in terms of E op As a result, the exposure energy required for pattern formation increased.

[0136] 5) Measurement of dielectric constant The dielectric constant was measured using a PNA-L Network Analyzer N5230A (Agilent) and a Split Post Dielectric Resonator (QWED). Specifically, a film sample measuring 5cm x 5cm or more was prepared. The PNA-L Network Analyzer N5230A was set to 10GHz. The Split Post Dielectric Resonator was checked for blank conditions. The resonant frequency and Q value were measured in the blank condition. The sample was placed in the SPD, the thickness value was entered, and the resonant frequency and Q value were measured. Based on this, the D k / D f The value can be calculated.

[0137] 6) Chemical resistance measurement Prepare a sample coated on a wafer. Measure the thickness before chemical resistance evaluation. Heat the RDL stripper solution on a hot plate at 70°C. Immerse the sample in the RDL stripper solution and wait for 1 minute. Once the time is up, rinse with running water. Measure the thickness after chemical resistance evaluation. After measurement, calculate the % change in thickness before and after chemical resistance evaluation. 5% or less:○, 5~10%:△, 10% or more:X

[0138] [Table 3]

[0139] In the case of Examples 1 to 10, which are photosensitive resin compositions according to the present invention in which the ratio of -F / -OH contained in the polyimide repeating unit is 2 or more and 5 or less, the dielectric constant D k and dielectric loss D f It has low viscosity and excellent chemical resistance.

[0140] In contrast, in Comparative Examples 1 to 5, where the ratio of -F / -OH is greater than 5, the chemical resistance is poor and the dielectric loss D fThe dielectric loss D was high and inferior to those of Examples 1 to 10. In particular, in Comparative Example 2, where the -F / -OH ratio was 33, the chemical resistance was evaluated as very poor. In addition, in Comparative Examples 6 and 7, where the -F / -OH ratio was less than 2, the chemical resistance was poor and the dielectric loss D f It was also a little expensive.

[0141] Therefore, in the photosensitive resin composition according to one embodiment of the present invention, the polyimide repeating unit contains -F and -OH functional groups, and the -F / -OH ratio of the repeating unit satisfies 2≦-F / -OH≦5. This has the advantages of being easily soluble in PGMEA, an environmentally friendly aqueous solvent, and being developable in TMAH, an aqueous developer. At the same time, the dielectric loss D f It has excellent physical properties such as elongation and chemical resistance. Although the present invention has been described above using limited examples, the present invention is not limited thereto, and it goes without saying that various modifications and variations can be made by a person having ordinary skill in the art to which the present invention pertains within the technical spirit of the present invention and the equivalent scope of the claims set forth below.

Claims

1. The polyimide includes a repeating unit represented by the following formulas 1 to 4: A photosensitive resin composition, wherein the ratio between the total number of -F functional groups and the total number of -OH functional groups contained in the repeating units represented by the chemical formulas 1 to 4 satisfies 2≦-F / -OH≦5. 【Chemical 1】 In the above formulas 1 to 4, A1 is a tetravalent aliphatic organic group, A2 is a tetravalent aromatic ring group, B1 is a divalent aromatic ring group, B2 is a flexible functional group, p1 to p4 are each independently an integer of 1 to 10,000, and at least one of A1, A2, B1, and B2 contains a -F, -OH, or -F and -OH functional group.

2. 2. The photosensitive resin composition according to claim 1, wherein the ratio of the total number of repeating units represented by the chemical formulas 1 and 3 to the total number of repeating units represented by the chemical formulas 2 and 4 is 0.01 to 1.

0.

3. 2. The photosensitive resin composition according to claim 1, wherein the ratio of the total number of repeating units represented by Chemical Formulas 1 and 3 to the total number of repeating units represented by Chemical Formulas 1 to 4 is 0.05 to 0.

5.

4. 2. The photosensitive resin composition according to claim 1, wherein the ratio of the total number of repeating units represented by the chemical formulas 3 and 4 to the total number of repeating units represented by the chemical formulas 1 to 4 is 0.05 to 0.

5.

5. 2. The photosensitive resin composition according to claim 1, wherein the tetravalent aliphatic organic group comprises one or more selected from the group consisting of a substituted or unsubstituted tetravalent aliphatic cyclic group, a group represented by the following Chemical Formula 5, and a group represented by the following Chemical Formula 6: 【Chemistry 2】 In the above formulas 5 and 6, L1 is a direct bond, a substituted or unsubstituted alkylene group, —O—, —SO ２ -, -CO-, or -OCO-; R1 to R6 are the same or different and each independently represent hydrogen, a substituted or unsubstituted alkyl group, or a carboxy group; m and n are 2; R5 are the same or different; and R6 are the same or different.

6. 2. The photosensitive resin composition according to claim 1, wherein the tetravalent aliphatic organic group includes one or more groups selected from the group consisting of the following chemical formulas: 【Chemistry 3】

7. 2. The photosensitive resin composition according to claim 1, wherein the tetravalent aromatic ring group comprises one or more selected from the group consisting of a substituted or unsubstituted tetravalent aromatic monocyclic ring and a group represented by the following Chemical Formula 7: 【Chemistry 4】 In the above formula 7, L2 is a direct bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, —O—, —SO ２ -, -CO-, or -OCO-; R1 and R2 are the same or different and each independently represent hydrogen, a substituted or unsubstituted alkyl group, or a carboxy group; m and n are the same or different and each independently represent an integer of 0 to 3; when m is 2 or greater, R1 are the same or different; and when n is 2 or greater, R2 are the same or different.

8. 2. The photosensitive resin composition according to claim 1, wherein the divalent aromatic ring group includes one or more selected from a substituted or unsubstituted divalent aromatic monocyclic ring, a group represented by the following chemical formula 8, and a group represented by the following chemical formula 9: 【Chemistry 5】 In the above formulas 8 and 9, L3 and L4 are the same or different and each independently represent a direct bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, —O—, —SO ２ -, -CO-, or -OCO-; R1 to R4 are the same or different and each independently represent hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a hydroxy group, or a substituted or unsubstituted amine group; m1, m2, n1, and n2 are the same or different and each independently represent an integer of 0 to 4; when m1 is 2 or greater, R1s are the same or different; when n1 is 2 or greater, R2s are the same or different; when m2 is 2 or greater, R3s are the same or different; and when n2 is 2 or greater, R4s are the same or different.

9. The photosensitive resin composition according to claim 1 , wherein the flexible functional group comprises at least one selected from the following formulas 10 to 13: 【Chemistry 6】 In the above formulas 10 to 13, X1 to X3 are the same or different and each independently represent -O- or -CH ２ -, La1 to La11 are the same or different and each independently represent a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, R1 to R6 are the same or different and each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, x, y, and z are each independently a real number from 0 to 50, and a1 is a real number from 1 to 30.

10. The photosensitive resin composition according to claim 1 , wherein the flexible functional group includes one or more selected from the following chemical formulas: 【Chemistry 7】 In the above formula, n is independently a real number from 1 to 30, and x, y, and z are independently a real number from 1 to 50.

11. The photosensitive resin composition according to claim 1 , further comprising at least one selected from the group consisting of a photosensitizer, a crosslinking agent, an antioxidant, a surfactant, and a solvent.

12. An insulating film comprising the photosensitive resin composition according to claim 1 or a cured product thereof.

13. A semiconductor device comprising the insulating film according to claim 12.

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