KR102261232B1 - Polyimide resin and negative type photosensitive resin composition comprising same - Google Patents

Abstract

The present invention relates to an electronic device including a polyimide resin having the structure of Formula 1, a negative photosensitive resin composition including the same, and an organic insulating film or photosensitive pattern formed from the negative photosensitive resin composition.

Description

Polyimide resin and a negative photosensitive resin composition comprising the same {POLYIMIDE RESIN AND NEGATIVE TYPE PHOTOSENSITIVE RESIN COMPOSITION COMPRISING SAME}

This application claims the benefit of the filing date of Korean Patent Application No. 10-2018-0085003 filed with the Korean Intellectual Property Office on July 20, 2018, the entire contents of which are incorporated herein by reference.

The present invention relates to a photosensitive resin composition, and more particularly, to a negative-type ring-closed polyimide resin having excellent solubility and no swelling during development, and a negative photosensitive resin composition comprising the same.

Photosensitive resin is a representative functional polymer material that has been put to practical use in the production of various precision electronic and information industrial products, and is currently being used importantly in the high-tech industry, especially in the production of semiconductors and displays. In general, a photosensitive resin refers to a polymer compound in which a change in physical properties such as solubility in a specific solvent, coloration, and curing occurs due to chemical change in molecular structure within a short period of time by irradiation with light. By using photosensitive resin, micro-precision processing is possible, energy and raw materials can be greatly reduced compared to thermal reaction processes, and work can be performed quickly and accurately in a small installation space, leading to advanced printing, semiconductor production, and display production. , photocurable surface coating materials, etc., are widely used in various precision electronic and information industries.

These photosensitive resins can be largely divided into negative and positive types. The negative photosensitive resin is a type in which the light-irradiated portion is insolubilized in the developer, and the positive type photosensitive resin is a type in which the light-irradiated portion is solubilized in the developer. to be.

The polymer used for the negative photosensitive resin is required to have high solubility in the developer solution for the exposed portion after selective exposure, and low or no solubility for the unexposed portion in the developer solution. These requirements are for precision electronics. In the field of information industry, there is a greater demand for extremely fine pattern formation.

Korean Patent Application Publication No. 2006-0020650

Keun-byoung Yoon et al., Synthesis and photosensitivity properties of soluble polyimides containing methacryloyl groups, J. Korean Ind. Eng. Chem, Vol. 17, No. 2, April 2006, 217-222

An object of the present invention is to provide a polyimide having a ring-closed structure having excellent solubility and no flattening during pattern formation using a negative photosensitive composition, and a negative photosensitive resin composition comprising the same.

Another object of the present invention is to provide an electronic device including an organic insulating film or a photosensitive pattern formed from the negative photosensitive resin composition.

An exemplary embodiment of the present invention provides a polyimide resin comprising a structure of the following formula (1).

[Formula 1]

In Formula 1,

X is a tetravalent organic group,

Y is a divalent to hexavalent organic group,

R _{3 To} R _{6 Are} the same as or different from each other and each independently hydrogen; Or a C1-C10 organic group including a photopolymerizable unsaturated group, m ₁ , m ₂ , k ₁ and k ₂ are each 0 or 1, 0 ≤ m ₁ +m ₂ +k ₁ +k ₂ ≤ 2,

L ₁ is a divalent organic group, an aromatic group, an aliphatic group, or a combination of an aromatic group and an aliphatic group, at least one carbon _{may be replaced with C(=O), SO 2} , NR, S, or O, R is an aryl group or an alkyl group, L ₁ may be substituted with a halogen group, a hydroxyl group, a carboxyl group, a thiol group, a sulfonic acid group or an alkyl group,

R ₁ is -S-, -O-, -CO ₂ - or -SO ₂ -,

R ₂ is represented by the following formula (2).

[Formula 2]

In Formula 2, R ₇ is hydrogen; Or an alkyl group having 1 to 4 carbon atoms, p is an integer of 1 to 10,

* in Formula 1 is a site connected to the main chain or terminal group of the polyimide resin, * in Formula 2 is _{a site connected to R 1} , and n is an integer of 1 or more.

Another exemplary embodiment of the present invention is the polyimide resin; photocurable polyfunctional acrylic compound; And it provides a negative photosensitive resin composition comprising a photoinitiator.

In addition, another exemplary embodiment of the present invention provides an electronic device including an organic insulating film or a photosensitive pattern formed from the negative photosensitive resin composition.

According to the exemplary embodiments described herein, the polyimide resin does not swell and has excellent solubility even in the process of developing a pattern after selective exposure when forming a pattern using the photosensitive resin composition. In addition, according to the embodiments described in the present specification, it exhibits high adhesion to a substrate used in a display device with a lower light quantity than the conventional positive photosensitive polyimide, and can form an ultra-fine pattern while having excellent mechanical properties. It is possible to provide an electronic device comprising a photosensitive resin composition and an organic insulating film or photosensitive pattern formed from the negative photosensitive resin composition.

1 shows a line pattern formed according to Example 1. As shown in FIG.
2 shows a photograph of a hole pattern formed in Example 1. FIG.

Hereinafter, a polyimide resin, a photosensitive resin composition, and an electric device according to specific embodiments of the present invention will be described in detail.

An exemplary embodiment of the present invention provides a polyimide resin including the unit of Formula 1 and the terminal group of Formula 2 above.

The present inventors found that the photosensitive resin containing the polyimide resin of the specific structure is a substrate used in a semiconductor device or a display device, for example, a metal substrate such as Au, Cu, Ni, Ti, or an inorganic material such as _{SiO 2 , SiNx} Through experiments, it was confirmed through experiments that high adhesion and adhesion to the substrate can be realized, and improved mechanical properties such as excellent heat resistance or chemical resistance can be formed, and an ultra-fine pattern can be easily formed, and the invention was completed.

In particular, the negative photosensitive resin composition does not use a polyimide precursor, which requires a high temperature thermosetting process (imidization process), but uses a polyimide resin capable of a solution process at a low temperature, thereby omitting the high temperature imidization process. have.

In addition, the present inventors have found that when a structure in which a photopolymerizable unsaturated group is bonded to a side chain of a polyimide having a ring-closed structure is used as a conventional polyimide, swelling or a decrease in solubility occurs due to cyclization of the side chain during development. found out In addition, when a ring closure polyimide and a monomer having a photopolymerizable polyfunctional group are used together, high energy is generated in the curing process by exposure because the polymer itself does not have a photopolymerizable group, which makes precise patterning difficult and increases the process cost. revealed that there is In addition, an attempt is made to introduce a polyamic ester type by attaching a photopolymerizable group (R) to the ring-opened position after ring-opening the acid anhydride ring-closed structure of the ring-closed polyimide, but this is It was found that the synthesis group (R) was detached and there was a problem of unstable dimensional stability and generation of gas.

However, the polyimide resin according to the embodiment of the present invention described above _{includes the structure of Formula 2 including a photopolymerizable unsaturated group in the R 2} portion of the terminal groups, so that the terminal group is ring closed with the main chain or a side chain bonded thereto even during development. Since no reaction occurs, swelling does not occur during development.

The polyimide resin may include an unreacted hydroxyl group (OH), a carboxyl group (COOH), a thiol group, or a sulfonic acid group in the terminal group, and such groups may provide excellent solubility.

According to an example, the polyimide resin may include R ₂ of Formula 2 in an equivalent amount of 5 to 30%. For example, in the case of including an amine end group, it may be included in an amount of 5 to 30% relative to the anhydride, and in the case of including an anhydride end group, 5 to 30% of the amine.

According to an exemplary embodiment, X in Formula 1 is not particularly limited as long as it is a tetravalent organic group, for example, a tetravalent aromatic organic group, a tetravalent aliphatic organic group, or a tetravalent organic group in which an aromatic group and an aliphatic group are connected to each other. A carbon may be replaced by C(=O), SO ₂ , NR, S, or O, and R is an aryl group or an alkyl group. X specifically has the following structural formulas.

로는 하기 구조식들이 있다. In Formula 1, Y is a divalent to hexavalent organic group, and may be a divalent to hexavalent aromatic organic group, a divalent to hexavalent aliphatic organic group, or a divalent to hexavalent organic group in which an aromatic group and an aliphatic group are connected to each other. and at least one carbon may be replaced by C (=O), SO ₂ , NR, S, or O, R is an aryl group or an alkyl group, Y is a halogen group, a hydroxyl group, a carboxyl group, a thiol group, a sulfonic acid group Or it may be substituted with an alkyl group. Specifically

has the following structural formulas.

Among the structural formulas, examples of Z include the following structural formulas.

As in the above structures, when m ₁ +m ₂ +k ₁ +k ₂ is 1 or 2 and contains an OH or COOH group, the structure of Formula 2 is present in the side chain as well as the terminal of the polyimide resin to form a photosensitive film It is advantageous for improving the surface condition of the city.

In Formula 1, L ₁ is a divalent organic group, an aromatic group, an aliphatic group, or a combination of an aromatic group and an aliphatic group, and at least one carbon is C (=O), SO ₂ , NR, S, or O may be replaced, R is an aryl group or an alkyl group, and L ₁ may be substituted with a halogen group, a hydroxyl group, a carboxyl group, a thiol group, a sulfonic acid group or an alkyl group. Here, the aromatic group may be a C6-C20 arylene group, and the aliphatic group may be a C1 to C20 alkylene group, or a C3 to C20 cycloalkylene group. Examples of the arylene group include a phenylene group. Examples of the halogen group include F.

According to an exemplary embodiment, L ₁ may be a phenylene group.

According to an exemplary embodiment, the structure of Formula 1 may be represented by Formula 11 or 12 below.

[Formula 11]

[Formula 12]

상기 화학식 11 및 12에 있어서, L₂는 2가 유기기이고, 나머지 치환기는 전술한 바와 같다.

In Formulas 11 and 12, L ₂ is a divalent organic group, and the remaining substituents are the same as described above.

According to one example, L ₂ may be alkylene or arylene, specifically C1 to C12 alkylene or phenylene.

According to an exemplary embodiment, R ₁ is -S-, -O-, or -CO ₂ -.

According to an exemplary embodiment, R _{1 is -S-.}

According to an exemplary embodiment, R ₁ is -O-.

According to an exemplary embodiment, R _{1 is —CO 2} —.

According to an exemplary embodiment, L ₂ is phenylene.

According to an exemplary embodiment, the polyimide resin may include two or more types of units represented by the formula (1), and may further include units other than the units of the formula (1) if necessary. However, it is preferable that the polyimide resin contains 50 mol% or more of the unit of Formula 1 above.

The other end of the polyimide resin may also have the end of Chemical Formula 2, and may have a diamine or dianhydride used in the preparation of the polyimide as a terminal group.

According to an exemplary embodiment, the polyimide resin may have a weight average molecular weight of 1,000 to 500,000, preferably 5,000 to 200,000. If the weight average molecular weight is less than 1,000, it may be difficult to implement the desired coating properties and mechanical properties when the polyimide copolymer is applied, and if it exceeds 500,000, the solubility in the developer is lowered, so that it may be difficult to apply as a photosensitive material. . The weight average molecular weight may be a value measured by gel permeation chromatography, that is, GPC.

The polyimide resin may be prepared using a dianhydride compound and a diamine compound, and materials and polymerization methods for constituting the polyimide may be those known in the art. However, in order to have a terminal group of Formula 1, a compound having at least one group selected from a hydroxyl group, a carboxyl group, a thiol group and a sulfonic acid group during polymerization of the polyimide, and one anhydride group or one amine group, by using a compound having a hydroxyl group, A polyimide having at least one group selected from a carboxyl group, a thiol group and a sulfonic acid group may be prepared, and the terminal group of Formula 1 may be prepared by reacting an isocyanate-based compound thereto.

Another exemplary embodiment of the present invention is the polyimide resin; photocurable polyfunctional acrylic compound; And it provides a negative photosensitive resin composition comprising a photoinitiator. The negative photosensitive resin composition may further include a solvent. If necessary, the negative photosensitive resin composition may further include an epoxy resin.

In the negative photosensitive resin composition of the embodiment, the photocurable 　 polyfunctional 　 acrylic compound is a compound having at least two photocurable acrylic structures in a molecule, specifically, an acrylate-based compound, a polyester acrylate-based compound, and a polyurethane It may include at least one acrylic compound selected from the group consisting of an acrylate-based compound, an epoxy acrylate-based compound, and a caprolactone-modified acrylate-based compound.

For example, as the acrylate-based compound, a hydroxyl group-containing acrylate-based compound such as pentaerythritol triacrylate or dipentaerythritol pentaacrylate; and a water-soluble acrylate compound such as polyethylene glycol diacrylate or polypropylene glycol diacrylate, and examples of the polyester acrylate compound include trimethylolpropane triacrylate, pentaerythritol tetraacrylate, or di Pentaerythritol hexaacrylate etc. are mentioned. In addition, examples of the polyurethane acrylate compound include isocyanate-modified products of the hydroxyl group-containing acrylate compound. Examples of the epoxy acrylate compound include bisphenol A diglycidyl ether and hydrogenated bisphenol A diglyceride. (meth)acrylic acid adduct of cydyl ether or phenol novolak epoxy resin, etc. are mentioned, The caprolactone-modified acrylate-based compound includes caprolactone-modified ditrimethylolpropane tetraacrylate, ε-caprolactone-modified dipenta The acrylate of erythritol, caprolactone-modified hydroxypivalic acid neopentyl glycol ester diacrylate, etc. are mentioned.

In addition, in the negative photosensitive resin composition of the embodiment, the epoxy resin may serve to help exhibit high adhesion and adhesion to a substrate used for a semiconductor device or a display device, and the epoxy resin may be subjected to a low-temperature curing process Therefore, there is a characteristic that can also improve the economic feasibility of the process.

Examples of the epoxy resin include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, brominated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, novolak epoxy resin, phenol furnace Volak type epoxy resin, cresol novolak type epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolak type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, chelate type epoxy resin, glyoxal type epoxy Resin, amino group-containing epoxy resin, rubber-modified epoxy resin, dicyclopentadiene phenolic type epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, tetraglycidyl xylenoyl ethane resin, silicone-modified epoxy resin and ε- It may include at least one selected from the group consisting of caprolactone-modified epoxy resins, and preferably may include a liquid N-glycidyl epoxy resin.

In addition, as the photo-initiator in the negative photosensitive resin composition of the embodiment, as long as it is known to be commonly used in the photosensitive resin composition, it may be used without any particular limitation, and in consideration of the wavelength of ultraviolet light used, the photo-initiator may be used. can be appropriately selected. As the photopolymerization initiator, for example, an acetophenone-based compound, a biimidazole-based compound, a triazine-based compound, an oxime-based compound, or a mixture thereof may be used.

Specific examples of the photopolymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4 -(2-hydroxyethoxy)-phenyl-(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, benzoinmethyl ether, benzoinethyl ether, benzoinisobutyl ether, benzoin Inbutyl ether, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl-(4-methylthio)phenyl-2-morpholino-1-propan-1-one, 2-benzyl-2-dimethyl Acetophen, such as amino-1-(4-morpholinophenyl)-butan-1-one, or 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one acetophenone compounds; 2,2-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl biimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5' -tetrakis (3,4,5-trimethoxyphenyl) -1,2'-biimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4',5,5'- Biimidazole compounds such as tetraphenyl biimidazole or 2,2'-bis(o-chlorophenyl)-4,4,5,5'-tetraphenyl-1,2'-biimidazole ; 3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionic acid, 1,1,1,3,3,3-hexafluoroisopropyl -3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionate, ethyl-2-{4-[2,4-bis(trichloro methyl)-s-triazin-6-yl]phenylthio}acetate, 2-epoxyethyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio }acetate, cyclohexyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, benzyl-2-{4-[2,4-bis (trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, 3-{chloro-4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio }propionic acid, 3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionamide, 2,4-bis(trichloromethyl)-6- p-methoxystyryl-s-triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl)-1,3,-butadienyl-s-triazine, or triazine-based compounds such as 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine; and oxime-based compounds such as CGI-242 and CGI-124 manufactured by Shiba in Japan.

In addition, the negative photosensitive resin composition according to the exemplary embodiment may include 10 to 50 parts by weight of the photocurable polyfunctional acrylic compound and 0.1 to 10 parts by weight of the photoinitiator based on 100 parts by weight of the polyimide resin. The composition may further include 10 to 100 parts by weight of an epoxy resin based on 100 parts by weight of the polyimide resin.

In addition, the negative photosensitive resin composition may further include one or more curing accelerators selected from the group consisting of an imidazole-based compound, a phosphine-based compound, and a tertiary amine compound. The imidazole-based compound may be, for example, 2-phenylimidazole, 2-phenyl-4-methylimidazole, or 2-phenyl-4-methyl-5-hydroxymethylimidazole, and a phosphine-based compound. may be, for example, triphenylphosphine, diphenylphosphine, phenylphosphine, tetraphenylphosphonium tetraphenylborate, and the tertiary amine compound is, for example, dicyandiamide, benzyldimethylamine, 4 -(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine. The curing accelerator may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polyimide resin.

Meanwhile, the negative photosensitive resin composition may further include a solvent, an adhesion promoter, a surfactant, an antifoaming agent, a leveling agent, an anti-gelling agent, or a mixture thereof.

As the solvent, an organic solvent known to be used in the negative photosensitive resin composition may be used without any particular limitation, but preferably ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl Methoxy propionate, ethyl ethoxy propionate (EEP), ethyl lactate, propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl cellosolve acetate , Diethylene glycol methyl acetate, diethylene glycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexanone, dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrol Don (NMP), ν-butyrolactone (GBL), diethyl ether, ethylene glycol dimethyl ether, diglyme, tetrahydrofuran (THF), methanol, ethanol, propanol, iso-propanol, methyl cello Solve, ethyl cellosolve, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexane, heptane and octane alone or in combination with two solvents The above can be mixed and used. The organic solvent may be included in an amount of 100 parts by weight to 400 parts by weight based on 100 parts by weight of the polyimide resin.

In addition, as the adhesion promoter, a silane coupling agent having a functional group such as epoxy, carboxyl group or isocyanate may be used, and specific examples thereof include trimethoxysilyl benzoic acid, triethoxysilyl benzoic acid, etc. , γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-Glycidoxypropyltrimethoxysilane , gamma-glycidoxypropyltriethoxysilane, or a mixture thereof. The adhesion promoter may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polyimide resin.

In addition, the surfactant can be used without any particular limitation as long as it is known to be usable in the photosensitive resin composition, but it is preferable to use a fluorine-based surfactant or a silicone-based surfactant. The surfactant may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the polyimide resin.

Meanwhile, according to another embodiment of the present invention, an electric device including an organic insulating film or a photosensitive pattern formed from the negative photosensitive resin composition of the embodiment may be provided.

The organic insulating film or the photosensitive pattern includes a polyimide having a specific structure and an acrylic compound including two or more photocurable acrylic functional groups, and a substrate used in a semiconductor device or a display device, for example Au, Cu, Ni, High adhesion to a metal substrate such as Ti or _{an inorganic substrate such as SiO 2} , SiNx may be realized, and improved mechanical properties such as excellent heat resistance, insulation or chemical resistance may be obtained.

Therefore, the electric device including the organic insulating film or the photosensitive pattern formed from the negative photosensitive resin composition can realize excellent performance such as high resolution and high sensitivity, and exhibit excellent film properties and high mechanical properties, as well as excellent heat resistance properties. , for example, even when used for a long period of time or exposed for a long time in high temperature conditions, it is possible to implement a characteristic that the adhesion of the organic insulating film or the photosensitive pattern is not deteriorated and can be firmly maintained.

The organic insulating layer may include various insulating layers of a semiconductor device or a display device, for example, an interlayer insulating layer, a surface protection layer, a substrate electrode protection layer, a buffer coating layer, or a passivation layer. In addition, the electric device may include various components of a semiconductor device or a display device.

On the other hand, the organic insulating film or the photosensitive pattern, coating the negative photosensitive resin composition on a support substrate and drying to form a resin film; exposing the resin film; It may be formed through the steps of developing the exposed resin film with a developer and heat-treating the developed photosensitive resin film.

If the negative photosensitive resin composition is used, a patterned photosensitive resin film can be easily formed on a substrate such as glass or a silicon wafer. In this case, a method of applying the negative photosensitive resin composition is spin coating (spin coating). ), bar coating, screen printing, etc. may be used.

The supporting substrate that can be used in the process of forming the photosensitive resin film can be used without any particular limitation as long as it is known to be commonly used in the field of electronic communication, semiconductor, or display. A ceramic substrate, a polymer substrate, etc. are mentioned.

In the drying process after the application, the solvent is volatilized by prebaking at 50° C. to 150° C. for about 1 to 20 minutes, thereby forming a prebaked film. If the drying temperature is too low, the amount of the remaining solvent is too large, resulting in film loss in the non-exposed area during development, and the remaining film may be lowered. If the drying temperature is too high, the curing reaction is accelerated and the unexposed area may not be developed. can

In the step of exposing the resin film, ultraviolet or visible light having a wavelength of 200 to 500 nm may be irradiated using a photomask having a pattern to be processed, and the exposure amount is preferably 10 mJ/cm 2 to 4,000 mJ/cm 2 . The exposure time is also not particularly limited, and may be appropriately changed depending on the exposure apparatus used, the wavelength of the irradiated light, or the exposure amount. Specifically, the exposure time may be changed within the range of 5 to 250 seconds.

In the step of forming the photosensitive resin film, an alkaline aqueous developer generally known to be usable in the step of producing a semiconductor or display may be used without any particular limitation.

The present invention will be described in more detail in the following examples. However, the following examples only illustrate the present invention, and the content of the present invention is not limited by the following examples.

Synthesis Example 1

While passing nitrogen through a three-necked flask equipped with a stirrer, temperature control device, nitrogen gas injection device, dean-stark distillation and a cooler, 2,2'-bis(3-amino-4-) Cyphenyl) hexafluoropropane [2,2'-Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane] (BisAPAF) 16.02 g (43.75 mmol) was dissolved in GBL (gamma butyroloactone) 60 g. Then, 10.58 g (34.12 mmol) of 4,4'-Oxydiphthalic anhydride (ODPA) and 3.67 g (19.25 mmol) of trimellitic anhydride were added to the solution, followed by 4 hours. stirred. Thereafter, 20 g of toluene, 20 g of GBL, 0.84 g of aceticanhydride, and 2.12 g of aniline were added, the reaction temperature was raised to 160° C., and water was removed through a Dean-Stark distillation apparatus for 5 hours for 20 hours. reacted. After completion of the reaction, SPI-1, 104 g was obtained. After slowly adding 3 g (21 mmol) of 2-acryloyloxyetyl isocyanate to 100 g of the obtained SPI-1, the reaction temperature was raised to 60° C., and the mixture was stirred for 12 hours. As a result of 1H-NMR analysis, an average of 0.20 equivalents per hydroxyl group (-OH) in the polyimide was substituted with AOI to obtain SPI-A-1. The molecular weight of the polyimide resin was measured through Gel Permeation Chromtography (GPC) in a dimethylformamide (DMF) solvent, and the weight average molecular weight was found to be 14,000.

Synthesis Example 2

In Synthesis Example 1, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride [4,4-( hexafluoroisopropylidene)diphthalic anhydride] (6FDA) 15.16 g (34.12 mmol) was used to prepare polyimide resin SPI-3 in the same manner. After slowly adding 3 g (21 mmol) of 2-acryloyloxyetyl isocyanate to 100 g of the obtained SPI-3, the reaction temperature was raised to 60° C., and the mixture was stirred for 12 hours. As a result of 1H-NMR analysis, an average of 0.21 equivalents per hydroxyl group (-OH) in the polyimide was substituted with AOI to obtain SPI-A-2. The molecular weight of this polyimide resin was measured through Gel Permeation Chromtography (GPC) in a dimethylformamide (DMF) solvent, and the weight average molecular weight was found to be 16,000.

Synthesis Example 3

In Synthesis Example 1, instead of 4,4'-Oxydiphthalic anhydride (ODPA), 10.04 g (34.12 mmol) of biphenyltetracarboxylic dianhydride (BPDA) was used. A polyimide resin SPI-4 was prepared in the same manner except that it was used. After slowly adding 3 g (21 mmol) of 2-acryloyloxyetyl isocyanate to 100 g of the obtained SPI-4, the reaction temperature was raised to 60° C., and the mixture was stirred for 12 hours. As a result of 1H-NMR analysis, an average of 0.25 equivalents per hydroxyl group (-OH) in the polyimide was substituted with AOI to obtain SPI-A-3. The molecular weight of the polyimide resin was measured through Gel Permeation Chromtography (GPC) in a dimethylformamide (DMF) solvent, and the weight average molecular weight was found to be 15,000.

Synthesis Example 4

Polyimide resin SPI-2 was prepared in the same manner as in Synthesis Example 1, except that 3.69 g (19.25 mmol) of 1,2-cyclohexanedicaroxylic anhydride (CHA) was used instead of trimellitic anhydride. prepared. After slowly adding 3 g (21 mmol) of 2-acryloyloxyetyl isocyanate to 100 g of the obtained SPI-2, the reaction temperature was raised to 60° C., and the mixture was stirred for 12 hours. As a result of 1H-NMR analysis, an average of 0.23 equivalents per hydroxyl group (-OH) in the polyimide was substituted with AOI to obtain SPI-A-4. The molecular weight of this polyimide resin was measured through Gel Permeation Chromtography (GPC) in a dimethylformamide (DMF) solvent, and the weight average molecular weight was found to be 13,000.

Synthesis Example 5

In Synthesis Example 1, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride [4,4-( hexafluoroisopropylidene) diphthalic anhydride] (6FDA) 19.43 g (43.75 mmol) was used, and 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane [2,2'-Bis (3- The content of amino-4-hydroxyphenyl)-hexafluoropropane] (BisAPAF) was 13.46 g (36.75 mmol) instead of 16.02 g (43.75 mmol), and 1.53 g (14.00 mmol) of 4-aminophenol was used instead of trimellitic anhydride. Except that, polyimide resin SPI-5 was prepared in the same manner. After slowly adding 3 g (21 mmol) of 2-acryloyloxyetyl isocyanate to 100 g of the obtained SPI-5, the reaction temperature was raised to 60° C., and the mixture was stirred for 12 hours. As a result of 1H-NMR analysis, an average of 0.23 equivalents per hydroxyl group (-OH) in polyimide was substituted with AOI to obtain SPI-A-5. The molecular weight of the polyimide resin was measured through Gel Permeation Chromtography (GPC) in a dimethylformamide (DMF) solvent, and the weight average molecular weight was found to be 12,000.

Synthesis Example 6

Polyimide resin SPI-6 was prepared in the same manner as in Synthesis Example 5, except that 1.75 g (14.00 mmol) of 4-aminobenzenethiol was used instead of 4-aminophenol. . After slowly adding 3 g (21 mmol) of 2-acryloyloxyetyl isocyanate to 100 g of the obtained SPI-6, the reaction temperature was raised to 60° C., and the mixture was stirred for 12 hours. As a result of 1H-NMR analysis, an average of 0.23 equivalents per hydroxyl group (-OH) in the polyimide was substituted with AOI to obtain SPI-A-6. The molecular weight of this polyimide resin was measured through Gel Permeation Chromtography (GPC) in a dimethylformamide (DMF) solvent, and the weight average molecular weight was found to be 13,000.

Synthesis Example 7

In Synthesis Example 5, in the same manner except that 2.63 g (14.00 mmol) of N- (4-aminophenyl) maleimide was used instead of 4-aminophenol (4-aminophenol). A polyimide resin SPI-7 was prepared. After slowly adding 3 g (21 mmol) of 2-acryloyloxyetyl isocyanate to 100 g of the obtained SPI-7, the reaction temperature was raised to 60° C., and the mixture was stirred for 12 hours. As a result of 1H-NMR analysis, an average of 0.23 equivalents per hydroxyl group (-OH) in polyimide was substituted with AOI to obtain SPI-A-7. The molecular weight of this polyimide resin was measured through Gel Permeation Chromtography (GPC) in a dimethylformamide (DMF) solvent, and the weight average molecular weight was found to be 13,000.

Synthesis Example 8

Polyimide resin SPI-8 was prepared in the same manner as in Synthesis Example 5, except that 1.64 g (14.00 mmol) of 4-ethylaniline was used instead of 4-aminophenol. After slowly adding 3 g (21 mmol) of 2-acryloyloxyetyl isocyanate to 100 g of the obtained SPI-8, the reaction temperature was raised to 60° C., and the mixture was stirred for 12 hours. As a result of 1H-NMR analysis, an average of 0.23 equivalents per hydroxyl group (-OH) in polyimide was substituted with AOI to obtain SPI-A-8. The molecular weight of the polyimide resin was measured through Gel Permeation Chromtography (GPC) in a dimethylformamide (DMF) solvent, and the weight average molecular weight was found to be 12,000.

Synthesis Example 9

Dissolve 1 mol of 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB) in 80 g of diethylformamide (DEF), and 4,4'-oxydiphthalic dianhydride 1.1 mol of (4,4'-Oxydiphthalic anhydride) (ODPA) was added, put into 50 g of diethylformamide (DEF), and polymerized at 50° C. for 24 hours to prepare a solution containing polyamic acid. 40 g of toluene was added to the prepared solution and installed to remove water through a Dean-Stark distillation, followed by refluxing at 180° C. for 12 hours. The prepared polyimide solution was precipitated with a methanol solvent, and then dried. Then, the dried polyimide was dissolved in 50 g of diethylformamide (DEF) and then 2-methacryloyloxyethyl isocyanate (2-Methacryloyloxyethyl isocyanate) 3 mol was added, and 30 g of diethylformamide (DEF) was added and reacted at room temperature for 24 hours, and then a precipitate was formed in methanol and dried to obtain PI-M-1. The molecular weight was measured through Gel Permeation Chromtography (GPC) in a dimethylformamide (DMF) solvent, and the weight average molecular weight was found to be 17,000.

Example 1

10.0 g of polyimide resin SPI-A-1 of Synthesis Example 1, 0.45 g of Irgacure 369 (Ciba Specialty chemical) as a photoinitiator, and 2.0 g of photocurable polyfunctional acrylic compound Kayarrad DPHA (Nippon Kayaku) as an organic solvent MEDG After dissolving in 20 g of (Diethyleneglycol methyethyl ether), 0.05 g of DC-190 (Toray Dow Corning) was mixed and stirred at room temperature for 1 hour. After the stirring was completed, the obtained resultant was filtered through a filter having a pore size of 0.45 μm to prepare a photosensitive resin composition.

Example 2

A photosensitive resin composition was prepared in the same manner as in Example 1, except that 10 g of SPI-A-2 was used instead of the polyimide resin SPI-A-1 in Example 1.

Example 3

A photosensitive resin composition was prepared in the same manner as in Example 1, except that 10 g of SPI-A-3 was used instead of the polyimide resin SPI-A-1 in Example 1.

Example 4

A photosensitive resin composition was prepared in the same manner as in Example 1, except that 10 g of SPI-A-5 was used instead of the polyimide resin SPI-A-1 in Example 1.

Example 5

A photosensitive resin composition was prepared in the same manner as in Example 1, except that 10 g of SPI-A-6 was used instead of the polyimide resin SPI-A-1 in Example 1.

Comparative Example 1

A photosensitive resin composition was prepared in the same manner as in Example 1, except that 10 g of SPI-A-4 was used instead of the polyimide resin SPI-A-1 in Example 1.

Comparative Example 2

A photosensitive resin composition was prepared in the same manner as in Example 1, except that 10 g of SPI-1 without introducing a urethane acrylic functional group was used instead of the polyimide resin SPI-A-1 in Example 1.

Comparative Example 3

A photosensitive resin composition was prepared in the same manner as in Example 1, except that 10 g of SPI-2 without introducing a urethane acrylic functional group was used instead of the polyimide resin SPI-A-1 in Example 1.

Comparative Example 4

A photosensitive resin composition was prepared in the same manner as in Example 1, except that 10 g of SPI-A-7 was used instead of the polyimide resin SPI-A-1 in Example 1.

Comparative Example 5

A photosensitive resin composition was prepared in the same manner as in Example 1, except that 10 g of SPI-A-8 was used instead of the polyimide resin SPI-A-1 in Example 1.

Comparative Example 6

A photosensitive resin composition was prepared in the same manner as in Example 1, except that 10 g of PI-M-1 was used instead of the polyimide resin SPI-A-1 in Example 1.

Experimental Example: Photosensitivity test of photosensitive resin film

The photosensitive resin composition obtained in Examples and Comparative Examples was coated on a 10 cm x 10 cm glass substrate using a spin coating method of 800 rpm to 1,200 rpm, and then dried at 120° C. for 2 minutes to have a thickness of 5 μm. A substrate on which a film was formed was obtained. Then, using a mask on which a fine pattern was formed, exposure was performed at an energy of 40 mJ/cm 2 in a broadband aligner exposure apparatus. Thereafter, the exposed glass substrate was developed in a 2.38 wt% aqueous solution of tetramethyl ammonium hydroxide for 100 seconds, washed with ultrapure water, and dried under nitrogen to form a pattern on the photosensitive resin film. Then, the thickness of the exposed film was measured using the alpha step.

Whether or not a fine hole pattern having a diameter of 3 μm or less was implemented in the photosensitive resin film was evaluated. The state of the surface after coating or development was measured using an AFM (Atomic Force Microscope) without pinholes or cracks when observed with an optical microscope. When the uniformity of the surface was 0.5 nm or less, it was evaluated as high, otherwise, it was evaluated as low. The implementation of the hole pattern was evaluated as possible when a hole having a diameter of 3 μm or less was formed, and as poor when a residual film was left or the pattern was not formed due to non-development.

The measurement results are shown in Table 1 below. 1 shows a line pattern formed according to Example 1. 2 is a photograph showing that a hole pattern having a diameter of 3 μm or less formed in Example 1 is clearly formed.

Evaluation of photosensitive properties after coating
surface condition after development
surface condition Realization of hole patterns with a diameter of 3㎛ or less Example 1 Prize Prize possible Example 2 Prize Prize possible Example 3 Prize Prize possible Example 4 Prize Prize possible Example 5 Prize Prize possible Comparative Example 1 Prize Prize bad Comparative Example 2 Prize ha bad Comparative Example 3 Prize ha bad Comparative Example 4 Prize Prize bad Comparative Example 5 Prize Prize bad Comparative Example 6 Prize Prize bad

Comparative Example 1 had a terminal group of Chemical Formula 2 only in the side chain, and had a good surface state, but a poor hole pattern implementation state with a diameter of 3 μm or less. Comparative Examples 2 and 3 did not include the structure of Formula 2 at either the side chain or the terminal, and not only had a poor surface condition after development due to low swelling and solubility during development, but also poor implementation of hole patterns with a diameter of 3 μm or less. did. Comparative Examples 4 to 6 have a terminal group of Chemical Formula 2 in a side chain and a photocurable group at the terminal, and have good surface conditions, but poor implementation of hole patterns with a diameter of 3 μm or less. In particular, Comparative Example 6 was not developed in the developer due to the lack of alkali-soluble groups after photocuring. On the other hand, in Examples 1 to 5, the surface state after coating and after development was excellent, and it was possible to implement hole patterns with a diameter of 3 μm or less.

Claims (9)

A polyimide resin comprising the structure of Formula 11 or 12:
[Formula 11]

[Formula 12]

In Formulas 11 and 12,
X is a tetravalent organic group,
Y is a divalent to tetravalent organic group,
R _{3 To} R _{6 Are} the same as or different from each other and each independently hydrogen; Or a C1-C10 organic group including a photopolymerizable unsaturated group, m ₁ , m ₂ , k ₁ and k ₂ are each 0 or 1, 0 ≤ m ₁ +m ₂ +k ₁ +k ₂ ≤ 2,
L ₂ is a divalent organic group,
R ₁ is -S-, -O-, -CO ₂ - or -SO ₂ -,
R ₂ is represented by the following formula (2),
[Formula 2]

In Formula 2,
R ₇ is hydrogen; Or an alkyl group having 1 to 4 carbon atoms, p is an integer of 1 to 10,
* in Formula 1 is a site connected to the main chain or terminal group of the polyimide resin, * in Formula 2 is _{a site connected to R 1} , and n is an integer of 1 or more. delete The polyimide resin according to claim 1, wherein R ₁ is -S-, -O- or -CO _{2 -.} The polyimide resin according to claim 1, wherein L _{2 is phenylene.} The polyimide resin according to claim 1, wherein the polyimide resin has a weight average molecular weight of 1,000 to 500,000. The polyimide resin according to any one of claims 1 and 3 to 5; photocurable polyfunctional acrylic compound; And a negative photosensitive resin composition comprising a photoinitiator. The negative photosensitive resin composition according to claim 6, further comprising an organic solvent. The negative photosensitive resin composition of claim 6, wherein the photocurable polyfunctional acrylic compound is included in an amount of 10 to 50 parts by weight, and the photopolymerization initiator is included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polyimide resin. An electronic device comprising an organic insulating film or a photosensitive pattern formed from the negative photosensitive resin composition according to claim 6 .

Images