KR20130013202A - Photosensitive resin composition having improved moisture resistance - Google Patents

Abstract

PURPOSE: A photosensitive resin composition is provided to have high sensitivity by having high resolution and to have high photosensitivity. CONSTITUTION: A photosensitive resin composition comprises 15-95 weight% of polyimide indicated in chemical formula 1, 15-95 weight% of polyimide indicated in chemical formula 2, and 3-50 weight% of photoactive compound. In the chemical formula 1 and 2: each X1 and X2 is a tetravalent organic group which contains fluorine; X3 is a tetravalent organic group; Y1 is a divalent organic group which contains fluorine; each of Y2 and Y3 is a divalent organic group; 0<p≤1, 0≤q<1, p+q=1; n1 and n2 is an integer from 2-500; and each of E1-E4 is a polymer terminal group. The polyimide indicated in the chemical formula 1 comprises 60-100 equivalent of organic group contained based on the 100 equivalent of total organic groups.

Description

Photosensitive resin composition having improved moisture resistance

The present invention relates to providing a photosensitive resin composition excellent in hygroscopicity.

Polyimide is a polymer having a heteroimide ring in the main chain, and is prepared by condensation polymerization of tetracarboxylic acid and diamine.

Polyimide is of commercial importance because of its excellent light transmittance and excellent adhesion to mechanical properties, thermal properties and substrate. Polyimide is widely used to replace metal or glass in various fields such as electricity, electronics, automobiles, airplanes, and semiconductors.

Polyimide has been widely used as a protective film in the semiconductor industry because of its excellent electrical insulation. In recent years, as the size and density of integrated circuits have been accelerated, researches on using them as insulating layers and protective films of multilayer engines for high density integrated circuits have been actively conducted, and among them, research on polyimides usable for electronic materials having low water absorption rates is urgently needed. It is a required situation.

An object of the present invention is to provide a highly sensitive positive photosensitive resin composition having low water absorption and high solubility in an alkaline developer.

The photosensitive resin composition according to the present invention, based on the solid content, 15 to 95% by weight of polyimide represented by the following formula (1); 2 to 80% by weight of the polyimide represented by the following formula (2) and 3 to 50% by weight of the photoactive compound.

Formula 1

(2)

Here, X ₁ and X ₂ are tetravalent organic groups containing fluorine element, X ₃ is tetravalent organic group, Y ₁ is divalent organic group containing fluorine element, and Y ₂ and Y ₃ are divalent 0 <p ≦ 1, 0 ≦ q <1, p + q = 1, n ₁ and n ₂ are each an integer of 2 to 500, and E ₁ to E ₄ are polymer terminals.

More specifically, X ₁ and X ₂ of the polyimide represented by the formula (1) is a C6 ~ C60 tetravalent organic group containing a fluorine element, Y ₁ is a C6 ~ C30 divalent organic group containing a fluorine element, Y ₂ may be a divalent organic group of C6 to C60, X ₃ of the polyimide represented by Formula 2 may be a tetravalent organic group of C6 to C60, Y ₃ may be a divalent organic group of C6 to C60, It is not limited.

Polyimide according to the present invention is obtained by the reaction of dianhydride and diamine (dihydric), dianhydride and diamine containing fluorine element used to synthesize the polyimide represented by the formula (1) Organic group) is preferably included in an amount of 60 to 100 equivalents based on 100 dianhydrides and 100 equivalents of diamine (100 molar equivalents of total organic groups).

X ₁ and X ₂ of the polyimide represented by Formula 1 Are 2,2-bis (3,4-dicarboxyphenyl) hexafluoroisopropylidene dianhydride, 4,4'-hexafluoroisopropylidenediphthalic anhydride and 2,2-bis [4- ( A tetravalent organic group containing at least one fluorine element selected from the group consisting of 3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride may be used, but is not limited thereto.

X ₃ of the polyimide represented by Formula 2 Pyromellitic anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4 , 4'-diphenylethertetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride, butane-1,2,3,4-tetracarboxylic dianhydride , 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetra Methyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid Dianhydrides, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-cyclohexene-1 , 2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentane acetic dianhydride, bicyclo [2,2,2] octo-7-ene-2,3,5,6- Tetraca 1 type selected from the group consisting of acid dianhydrides, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydrides, 3,5,6-tricarboxy-2-norbornane acetic dianhydrides and derivatives thereof Although the tetravalent organic group mentioned above can be used, it is not limited to this.

Y ₁ of the polyimide represented by Formula ₁ Silver 3,5-diaminobenzotrifluoride, 2,2'-bis (trifluoromethyl) -4,4'-diamino biphenyl, 2,2-bis [4- (amidophenoxy) phenyl ] A divalent organic group containing at least one fluorine element selected from the group consisting of hexafluoropropane and 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane may be used. It is not.

Y ₂ and Y ₃ of the polyimide represented by Formulas 1 and 2, respectively,

Diamine containing a hydroxyl group selected from the group consisting of;

로 표시되는 카르복실기를 포함하는 디아민;

Diamine containing a carboxyl group represented by;

3,5-diaminobenzotrifluoride, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2-bis [4- (aminophenoxy) phenyl] hexa Fluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 3,5-diaminobenzoic acid, p-phenylenediamine, m-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4 -Phenylenediamine, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, 3,3'-diaminodiphenylether, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-methylene-bis (2-methylaniline), 4, 4'-methylene-bis (2,6-dimethylaniline), 4,4'-methylene-bis (2,6-diethylaniline), 4,4'-methylene-bis (2-isopropyl-6-methyl Aniline), 4,4'-methylene-bis (2,6-diisopropylaniline), 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, benzidine, o-tolidine , m-tolidine, 3,3 ', 5,5'-tetramethylbenzidine, 2,2'-bis (trifluoromethyl) benzidine, 1,4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy Phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 2,2-bis [4- (3 Aromatic diamine selected from the group consisting of -aminophenoxy) phenyl] propane; And

1,6-hexadiamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 4,4 One or more diamines selected from the group consisting of aliphatic diamines selected from the group consisting of '-diaminodicyclohexylmethane and 4,4'-diamino-3,3'-dimethyldicyclohexylmethane can be used but are now limited It doesn't happen.

E ₁ to E ₄ of the polyimide represented by Formulas 1 and 2 are 4-aminophenol, N- (4-aminophenyl) maleimide, 4-ethynylaniline, maleic anhydride, 5-norbornene- At least one selected from the group consisting of 2,3-dicarboxylic acid anhydride, 1,2-cyclohexanedicarboxylic acid anhydride, n-octylsuccinic anhydride, 4-thiolaniline, 4-phenylethynyl phthalic anhydride Polymer terminals may be used, but are not limited thereto.

The photoactive compound is an o-quinone diazide derivative, 1,2-naphthoquinone diazide derivative, allyl diazonium salt, diallyl iodonium salt, triallylsulfonium salt, o-nitrobenzyl ester, p-nitrobenzyl ester, tri One or more compounds selected from the group consisting of halomethyl group-substituted s-triazine derivatives, imidesulfonate derivatives, and the following formulas may be used alone or in a condensation reaction, but is not limited thereto.

E ranges from 1 to 1000 in repeat units.

The condensation reaction compound may be used one or more selected from the group consisting of the following formula, but is not limited thereto.

E ranges from 1 to 1000 in repeat units,

및 -OH 중 선택되는 하나이다.Where -OD is each

And -OH.

The photosensitive resin composition is N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine , Dimethyl sulfone, hexamethyl sulfoxide, m-cresol, γ-butyrolactone, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, butyl carbitol acetate, ethylene glycol, One or more solvents selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, butyl lactate, cyclohexanone, and cyclopentanone may be used, but is not limited thereto.

The photosensitive resin composition may further include at least one other additive selected from the group consisting of a curing agent, a dissolution rate regulator, a sensitizer, an adhesion enhancer, and a surfactant.

Moreover, this invention provides the photosensitive film formed using the said photosensitive resin composition.

The thickness of the photosensitive film may be in the range of 1 to 20㎛.

The photosensitive film may include an interlayer insulating film, a passivation film, a buffer coat film, an insulating film for multilayer printed circuit boards, an insulating film for OLEDs, a protective film for thin film transistors for liquid crystal display devices, an electrode protective film for organic EL devices, and the like. It may be used for one or more uses selected from the group consisting of a semiconductor protective film, but is not limited thereto.

Positive type photosensitive resin composition containing the polyimide proposed by this invention has the effect of low water absorption and high photosensitivity.

The present invention provides a photosensitive resin composition by mixing a polyimide represented by the following formula (1) and a polyimide represented by the following formula (2) at an optimum ratio, and has a low water absorption and at the same time a high sensitivity positive to an alkaline developer. A type photosensitive resin composition can be implemented.

Hereinafter, the present invention will be described in detail.

The present invention relates to a photosensitive resin composition, specifically 15 to 95% by weight of a polyimide represented by the following formula (1) based on the solid content of the composition; The present invention relates to a photosensitive resin composition having excellent hygroscopicity, comprising 2 to 80% by weight of polyimide represented by Formula 2 and 3 to 50% by weight of a photoactive compound.

Formula 1

(2)

Here, X ₁ and X ₂ are tetravalent organic groups containing fluorine element, X ₃ is tetravalent organic group, Y ₁ is divalent organic group containing fluorine element, and Y ₂ and Y ₃ are divalent 0 <p ≦ 1, 0 ≦ q <1, p + q = 1, n ₁ and n ₂ are each an integer of 2 to 500, and E ₁ to E ₄ are polymer terminals.

More specifically, X ₁ and X ₂ of the polyimide represented by the formula (1) is a C6 ~ C60 tetravalent organic group containing a fluorine element, Y ₁ is a C6 ~ C30 divalent organic group containing a fluorine element, Y ₂ may be a divalent organic group of C6 to C60, X ₃ of the polyimide represented by Formula 2 may be a tetravalent organic group of C6 to C60, Y ₃ may be a divalent organic group of C6 to C60, It is not limited.

In the present invention, the photosensitive resin composition has a low water absorption and high sensitivity, in order to implement a positive photosensitive resin composition, 15 to 95 wt% based on solids of the polyimide photosensitive resin composition containing fluorine atom (F) represented by Formula 1 above; 2 to 80% by weight of the polyimide represented by the formula (2) is used, preferably 20 to 90% by weight of the polyimide represented by the formula (1) and 5 to 50% by weight of the polyimide represented by the formula (2) More preferably, 50 to 80% by weight of the polyimide represented by the formula (1) and 10 to 40% by weight of the polyimide represented by the formula (2) are used.

The polyimide according to the present invention is obtained by the reaction of dianhydride and diamine, and the polyimide represented by Chemical Formula 1 contains a dianhydride containing a fluorine element and a diamine containing or without a fluorine element. Can be synthesized.

The dianhydride containing fluorine element and the diamine (organic group containing fluorine element) containing the fluorine element used to synthesize the polyimide represented by the formula (1) are 100 dianhydride and 100 equivalents of diamine (100 molar total organic group) It is preferable to include 60 to 100 equivalents based on equivalent), and if it is less than this range, there is a problem that can not secure a low water absorption rate that can be used as an electronic material.

X ₁ of the polyimide represented by Formula ₁ X and X ₂ are each a tetravalent organic group containing a fluorine element, and may be used without limitation as long as it is a substance used in the art. Non-limiting examples include 2,2-bis (3,4-dicarboxyphenyl) hexafluoroisopropyl In the group consisting of: aidene dianhydride, 4,4'-hexafluoroisopropylidenediphthalic anhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride One or more types selected can be mentioned.

X ₃ of the polyimide represented by Chemical Formula 2 may be used without limitation as long as it is a substance used in the art as a tetravalent organic group. Examples thereof include pyromellitic anhydride, 3,3 ', 4,4'-biphenyltetra Carboxylic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride, butane-1,2,3,4-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1 , 2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetra Hydro-1-naphthalene succinic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl -Cyclohexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentane acetic dianhydride, bicyclo [2,2,2] octo-7-ene-2,3 , 5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 3,5,6-tricarboxy-2-norbornane acetic dianhydride and derivatives thereof And one or more selected from the group consisting of.

Y ₁ of the polyimide represented by Chemical Formula 1 may be used without limitation as long as it is a substance used in the art as a divalent organic group containing a fluorine element, and examples thereof include, but are not limited to, 3,5-diaminobenzotrifluoride, 2 , 2'-bis (trifluoromethyl) -4,4'-diamino biphenyl, 2,2-bis [4- (aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (3- And at least one selected from the group consisting of amino-4-hydroxyphenyl) hexafluoropropane and the like.

Y ₂ and Y ₃ of the polyimide represented by the general formulas (1) and (2) are each a bivalent organic group and can be used without limitation as long as it is a material used in the related art. For example, a diamine including a hydroxyl group, a diamine including a carboxyl group, Aromatic diamines and aliphatic diamines.

Specifically, the diamine containing the hydroxyl group

And one or more selected from the group consisting of.

등이 있다.Specifically, the diamine containing the carboxyl group

Etc.

Specifically, the aromatic diamine is 3,5-diaminobenzotrifluoride, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2-bis [4- (amino Phenoxy) phenyl] hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 3,5-diaminobenzoic acid, p-phenylenediamine, m-phenylenediamine , 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 4,4'-diaminodiphenylether, 3,4 '-Diaminodiphenylether, 3,3'-diaminodiphenylether, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylmethane, 3,4'-diaminodi Phenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-methylene-bis (2-methylaniline), 4,4'-methylene-bis (2,6-dimethylaniline), 4,4 ' -Methylene-bis (2,6-diethylaniline), 4,4'-methylene-bis (2-isopropyl-6-methylaniline), 4,4'-methylene-bis (2,6-diisopropyl Aniline), 4,4'-diaminodiphenyl Phon, 3,3'-diaminodiphenylsulfone, benzidine, o-tolidine, m-tolidine, 3,3 ', 5,5'-tetramethylbenzidine, 2,2'-bis (trifluoromethyl ) Benzidine, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- ( 4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 2,2-bis [ And one or more selected from the group consisting of 4- (3-aminophenoxy) phenyl] propane and the like.

Specifically, the aliphatic diamine is 1,6-hexadiamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) And at least one selected from the group consisting of cyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, and the like. However, Y ₂ and Y ₃ are not limited thereto.

E ₁ to E ₄ of the polyimide represented by Formulas 1 and 2 are each polymer terminal capping the ends of the polyimide, and any material used in the art can be used without limitation, but non-limiting example, 4-amino Phenol, N- (4-aminophenyl) maleimide, 4-ethynylaniline, maleic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 1 or more types chosen from the group which consists of n-octyl succinic anhydride, 4-thiol aniline, 4-phenylethynyl phthalic anhydride, etc. are mentioned.

The polyimide represented by Formulas 1 and 2 are each repeated by repeating units n ₁ and n ₂ , and each of n ₁ and n ₂ is preferably an integer ranging from 2 to 500. If the repeating units n ₁ and n ₂ is less than 2, there is a risk of not exhibiting sufficient mechanical and thermal stability, if n ₁ and n ₂ is too high exceeding 500 may be difficult to achieve a thin film coating and high resolution, high sensitivity have.

The photoactive compound of the present invention is a compound capable of generating an acid when it receives light, and serves to increase acid solubility in an alkaline developer by generating an acid by a photoreaction.

The photoactive compound is suitable to use 3 to 50% by weight of the solid content of the photosensitive resin composition, preferably 3 to 40% by weight, more preferably 5 to 30% by weight can be used. If the photoactive compound is less than 3% by weight, the adhesion to the substrate is lowered, and there is a problem that it is difficult to obtain a uniform coating property and a desired film thickness. If the photoactive compound is more than 50% by weight, it becomes more viscous than necessary to obtain a smooth surface during coating. Not only can not be difficult to evenly mix the photosensitive resin composition is difficult to implement the physical properties for forming a fine pattern is not preferred.

The photoactive compound is not particularly limited as long as it generates an acid by photoreaction, and specific examples thereof include o-quinonediazide derivatives, 1,2-naphthoquinonediazide derivatives, allyldiazonium salts, diallyl iodonium salts and triallyl. One or more compounds selected from the group consisting of sulfonium salts, o-nitrobenzyl esters, p-nitrobenzyl esters, trihalomethyl group-substituted s-triazine derivatives, imidesulfonate derivatives, and the following formulas: And one or more selected from the group consisting of.

E is a repeating unit and ranges from 1 to 1000.

In particular, the photoactive compound is preferably an o-quinone diazide derivative or a 1,2-naphthoquinone diazide derivative in terms of sensitivity and resolution.

The o-quinonediazide derivatives or 1,2-naphthoquinonediazide derivatives generally have sulfonyl chloride functional groups and are sulfonic acid esters or sulfones obtained by condensation reaction with a compound having a hydroxyl group or a compound having an amino group in the presence of a basic catalyst. Used in forms containing amides.

Especially, it is preferable to select and use from the group which consists of following formula.

및 -OH 중 선택되는 하나이다.E ranges from 1 to 1000 in repeat units and -OD is each

And -OH.

On the other hand, the solvent used for the photosensitive resin composition of this invention will not be specifically limited if it can dissolve high molecular compounds, such as said polyimide and polyamic acid. Specific examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl Sulfone, hexamethylsulfoxide, m-cresol, γ-butyrolactone, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butylcarbitol, ethylcarbitol acetate, butylcarbitol acetate, ethylene glycol, propylene glycol Monomethyl ether acetate (PGMEA), ethyl lactate, butyl lactate, cyclohexanone, cyclopentanone, and the like.

In addition to the components mentioned above, the photosensitive resin composition of the present invention may further include other additives such as a curing agent, a dissolution rate regulator, a sensitizer, an adhesion enhancer, and a surfactant.

The photosensitive film may be formed on a substrate such as a glass substrate or a silicon wafer using the positive photosensitive resin composition described above.

The method of forming the photosensitive film can be used without limitation the method used in the art.

As a specific example, the positive photosensitive resin composition is applied onto a substrate such as a glass substrate using a conventional method such as spin coating, slit spin coating, slit coating, roll coating, die coating, curtain coating, and the like. Form through. The exposure and development processes also use a method used in forming a photosensitive layer film using a conventional photosensitive resin composition, and are not particularly limited.

There is no restriction | limiting in particular as light irradiated from the said light irradiation means in the said exposure process, Although it can select suitably according to the objective, Visible light, an electron beam, an X-ray laser beam etc. are mentioned from an electromagnetic wave and an ultraviolet-ray.

The method of irradiating light by the light irradiating means is not particularly limited and may be appropriately selected in accordance with the purpose. Examples of the method include high pressure mercury lamps, xenon lamps, carbon arc lamps, halogen lamps, cold cathode tubes for radiators, For example, by a known light source.

The developing step is a step of forming a pattern by removing a region exposed by an exposure step with a developer. The developing solution is not particularly limited and may be appropriately selected according to the purpose. Examples of the developing solution include a hydroxide or carbonate of an alkali metal or an alkaline earth metal, a hydrogen carbonate, an aqueous ammonia solution and an aqueous solution of a quaternary ammonium salt. Among them, TMAH (Tetramethylammonium hydroxide) aqueous solution is particularly preferable.

The developer may be a surfactant, an antifoaming agent, an organic base (for example, benzylamine, ethylene diamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.); May be used in combination with an organic solvent (for example, alcohols, ketones, esters, ethers, amides, lactones, etc.) in order to promote development. The developing solution may be an aqueous developing solution obtained by mixing water or an alkali aqueous solution with an organic solvent, or may be an organic solvent alone.

The overall process is spin coating the photosensitive resin composition of the present invention onto glass and prebakeing at about 100 ° C. for 2 minutes to form a film. After exposing the film to an energy of 20-1000 mJ / cm ² under a high-pressure mercury lamp using a photomask, the pattern is developed using TMAH aqueous solution and washed with deionized water. After that, a postbake is performed at 200 to 350 ° C. for about 30 to 60 minutes to obtain a pattern.

The thickness of the photosensitive film thus obtained may vary depending on the purpose, but is preferably 1 to 20㎛, but is not limited thereto.

The photosensitive resin composition of the present invention has high sensitivity and high resolution positive photosensitive characteristics, and is easily etched by an aqueous alkali solution, and has a fine shape and a high dimensional accuracy relief pattern by exposing using a mask having a predetermined pattern. A photosensitive film can be obtained easily.

The positive type photosensitive resin composition of the present invention is not only an interlayer insulating film, a passivation film, a buffer coat film, an insulating film for multilayer printed circuit boards, an insulating film for OLED, but also a protective film for thin film transistors of liquid crystal display irradiation, It is suitable for use in electrode protective films, semiconductor protective films and the like of organic EL elements.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In addition, in the following examples, even if only one example of each component constituting the photosensitive resin composition according to the present invention is shown, it is apparent to those skilled in the art that the effect represented by various equivalents included in each component is similar.

Synthetic example  1: Preparation of Polyimide Represented by Formula (1)

11.0 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 40 g of γ-butyrolactone were sequentially added to a 100 mL round bottom flask, and slowly stirred to completely dissolve the flask. 13.3 g of 4,4'-hexafluoroisopropylidenediphthalic anhydride was slowly added while maintaining in water at room temperature. After the mixture solution was stirred at room temperature for 16 hours, 7 g of toluene was added thereto, and the mixture solution was installed to remove water through a dean-stark distillation and refluxed at 140 ° C. for 3 hours. The solution was cooled to room temperature, poured slowly into a methanol: water = 1: 4 mixture to solidify, and dried in a 40 ° C. vacuum drying oven for one day to obtain 20 g of polyimide resin.

The polyimide production peak was confirmed through IR, and the weight average molecular weight of the polyimide resin measured through GPC was 50,000, and the polydisperse index (PDI) was 1.7.

Synthetic example  2: Preparation of Polyimide Represented by Formula (2)

11.0 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 40 g of γ-butyrolactone were sequentially added to a 100 mL round bottom flask, and slowly stirred to completely dissolve the flask. 5.9 g of butane-1,2,3,4-tetracarboxylic dianhydride was slowly added while maintaining in water at room temperature. The mixed solution was stirred at room temperature for 16 hours, 7 g of toluene was added thereto, and installed to remove water through a dean-stark distillation, and then refluxed at 140 ° C. for 3 hours. The solution was cooled to room temperature, poured slowly into a methanol: water = 1: 4 mixture to solidify, and then dried in a 40 ° C. vacuum drying oven for one day to obtain 14 g of polyimide resin.

The polyimide formation peak was confirmed through IR, and the weight average molecular weight of the polyimide resin measured by GPC was 40,000 and the poly disperse index (PDI) was found to be 1.5.

Comparative Synthetic Example  One

11.0 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 40 g of γ-butyrolactone were sequentially added to a 100 mL round bottom flask, and slowly stirred to completely dissolve the flask. 9.7 g of 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride was slowly added while maintaining in water at room temperature. The mixed solution was stirred at room temperature for 16 hours, 7 g of toluene was added thereto, and installed to remove water through a dean-stark distillation, and then refluxed at 140 ° C. for 3 hours. The solution was cooled at room temperature, poured slowly into a methanol: water = 1: 4 mixture to solidify, and dried in a vacuum drying oven at 40 ° C. for one day to obtain 16 g of a soluble polyimide resin.

The polyimide formation peak was confirmed through IR, and the weight average molecular weight of the polyimide resin measured by GPC was 40,000 and the poly disperse index (PDI) was found to be 1.5.

Comparative Synthetic Example  2

6 g of 1,1-bis [4- (4-aminophenyl) methylphenyl] -4-n-butylcyclohexane in a 100 mL round bottom flask, 1,1-bis (4-aminophenoxy) phenyl-4- (4- 5 g of pentylcyclohexyl) cyclohexane and 40 g of γ-butyrolactone were sequentially added and slowly stirred to completely dissolve. Then, the flask was immersed in water and kept at room temperature, and 9.7 g of cyclobutane tetracarboxylic dianhydride was slowly added thereto. It was. The mixed solution was stirred at room temperature for 16 hours, 7 g of toluene was added thereto, and installed to remove water through a dean-stark distillation, and then refluxed at 140 ° C. for 3 hours. The solution was cooled to room temperature, poured slowly into a methanol: water = 1: 4 mixture to solidify, and dried in a vacuum drying oven at 40 ° C. for one day to obtain a soluble polyimide resin containing 16 g of side chain groups.

The polyimide formation peak was confirmed through IR, and the weight average molecular weight of the polyimide resin measured by GPC was 40,000 and the poly disperse index (PDI) was found to be 1.5.

Example  1: of photosensitive resin composition Manufacturing example  (Polyimide / polyimide Blending  Composition)

27.5 g of the polyimide synthesized in Synthesis Example 1 and 8.2 g of the polyimide synthesized in Synthesis Example 2 were mixed to prepare a mixture solution. Subsequently, a diazonaptoquinone ester compound represented by the following formula (3) as a photoactive compound in the mixture solution is optionally given among OH and OD according to the ratio of TPPA 320: OD / (OD + OH) = 2/3. g and 18 g of solvent γ-butyrolactone (GBL) were stirred at room temperature for 1 hour, and then filtered through a filter having a pore size of 1 μm to prepare a photosensitive resin composition.

(3)

Comparative example  1: of photosensitive resin composition Manufacturing example  (Polyimide Composition)

To 1.6 g of the soluble polyimide synthesized in Synthesis Example 1, 0.5 g of diazonaphthoquinone ester compound (TPPA 320) represented by Chemical Formula 3 and 4 g of a solvent γ-butyrolactone (GBL) were added as a photoactive compound. After stirring for a period of time, it was filtered through a filter having a pore size of 1 μm to prepare a photosensitive resin composition.

Comparative example  2: of photosensitive resin composition Manufacturing example  (Polyimide Composition)

To 1.6 g of the soluble polyimide synthesized in Comparative Synthesis Example 1 as a photoactive compound, 0.5 g of diazonaptoquinone ester compound (TPPA 320) represented by Formula 3 above, and 4 g of solvent γ-butyrolactone (GBL) were added at room temperature. After stirring for a period of time, it was filtered through a filter having a pore size of 1 μm to prepare a photosensitive resin composition.

Comparative example  3: of photosensitive resin composition Manufacturing example  (Polyimide Composition)

To 1.6 g of the soluble polyimide synthesized in Comparative Synthesis Example 2, 0.5 g of diazonaptoquinone ester compound (TPPA 320) represented by Chemical Formula 3 as a photoactive compound and 4 g of solvent γ-butyrolactone (GBL) were 1 at room temperature. After stirring for a period of time, it was filtered through a filter having a pore size of 1 μm to prepare a photosensitive resin composition.

Experimental Example

1. Photosensitivity evaluation

The photosensitive resin compositions prepared in Examples and Comparative Examples were spin coated on a 4 inch silicon wafer, and heated at 120 ° C. for 2 minutes on a hot plate to form a photosensitive film. After the vacuum heat-transfer contact the processed silicon wafer using the photomask, G-line stepper Nikon NSR was from 20mJ / cm ² to 1505 G4 to 5 mJ / cm ² with intervals 600 mJ / cm ² exposure in sequence. After developing at 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 80 seconds, it was washed and dried with ultrapure water for 60 seconds to obtain a pattern in which the non-exposed part remained clear. The silicon wafer thus patterned was gradually heated under a stream of nitrogen on a hot plate for about 30 minutes starting at room temperature until reaching 180 ° C., then held at 180 ° C. for 60 minutes, and then until 300 ° C. for 30 minutes. After slowly heating, the mixture was maintained at 300 ° C. for 60 minutes and heat treated.

The results of the photosensitivity evaluation are shown in Table 1 below.

Each composition had a thickness before exposure of 6 μm, in which Comparative Example 1 exhibited a sensitivity that was too slow to confirm sensitivity within the measurement range, but Example 1 blended two polyimides represented by Chemical Formulas 1 and 2 above. Shows a fast sensitivity of 300mJ / cm ² . Comparative compositions of Comparative Examples 2 and 3 was faster than the composition of Comparative Example 1 but showed a slow sensitivity compared to Example 1 it was confirmed that the sensitivity of the composition according to Example 1 is excellent.

division Water absorption (%) Sensitivity (mJ / cm ² ) Example 1 0.5 300 Comparative Example 1 0.3 > 600 Comparative Example 2 1.7 450 Comparative Example 3 1.5 550

2. Hygroscopicity evaluation

Each sample was coated with about 1 g of Examples and Comparative Examples in an Al dish, and then fired at 250 ° C. for 2 hr (oxygen <50 ppm). After the film of the prepared sample is left for 24 hours at constant temperature and constant humidity condition (85 ° C., 85% humidity condition), the absorption rate is measured by the weight before absorbing moisture at constant temperature and constant humidity condition and the weight change after absorbing moisture.

Percent of Absorption = (W2-W1) / W1 * 100

W1 = weight before immersion

W2 = weight after immersion

Hygroscopicity evaluation results are shown in Table 1 above.

Referring to Table 1, the composition of Comparative Example 1 having the highest content of fluorine-containing monomer shows the lowest absorption rate but shows the lowest sensitivity in the photosensitive evaluation. It was found difficult to obtain a resin composition.

In contrast, in the case of Example 1 blended two polyimide represented by the formulas (1) and (2), the moisture absorption rate tends to be slightly higher than that of Comparative Example 1, but it was confirmed that there is a high sensitivity characteristic with a significant difference from Comparative Example 1. .

In the case of Comparative Examples 2 and 3 showed a moisture absorption rate of more than 1%, it was confirmed that similar to the moisture absorption rate of the conventional polyimide.

As a result, it was confirmed that the photosensitive resin composition having low moisture absorption and high sensitivity could be prepared by blending polyimide having increased fluorine content and another polyimide that can adjust sensitivity.

Claims (16)

A photosensitive resin composition comprising a polyimide represented by the following Chemical Formula 1, a polyimide represented by the following Chemical Formula 2, and a photoactive compound:
Formula 1

(2)

Here, X ₁ and X ₂ are tetravalent organic groups containing fluorine element, X ₃ is tetravalent organic group, Y ₁ is divalent organic group containing fluorine element, and Y ₂ and Y ₃ are divalent 0 <p ≦ 1, 0 ≦ q <1, p + q = 1, n ₁ and n ₂ are each an integer of 2 to 500, and E ₁ to E ₄ are polymer terminals.
The method of claim 1,
15 to 95 wt% of the polyimide represented by Chemical Formula 1 based on the solids content of the composition; A photosensitive resin composition comprising 2 to 80% by weight of polyimide represented by the formula (2) and 3 to 50% by weight of the photoactive compound.
The method of claim 1,
The polyimide represented by the formula (1) is a photosensitive resin composition, characterized in that the organic group containing 60 to 100 equivalents containing fluorine element based on 100 equivalents of the total organic group.
The method of claim 1,
X ₁ and X ₂ of the polyimide represented by Formula 1 are C6 to C60 tetravalent organic groups containing fluorine element, Y ₁ is C6 to C30 divalent organic group containing fluorine element, Y ₂ Is a C6 to C60 divalent organic group, X ₃ of the polyimide represented by the formula (2) is a C6 to C60 tetravalent organic group, Y ₃ is a C6 to C60 divalent organic group, the photosensitive resin Composition.
The method of claim 1,
X ₁ and X ₂ of the polyimide represented by Formula 1 Are 2,2-bis (3,4-dicarboxyphenyl) hexafluoroisopropylidene dianhydride, 4,4'-hexafluoroisopropylidenediphthalic anhydride and 2,2-bis [4- ( 3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride A photosensitive resin composition characterized in that it is a tetravalent organic group containing at least one fluorine element selected from the group consisting of.
The method of claim 1,
X ₃ of the polyimide represented by Formula 2 Pyromellitic anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4 , 4'-diphenylethertetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride, butane-1,2,3,4-tetracarboxylic dianhydride , 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetra Methyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid Dianhydrides, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-cyclohexene-1 , 2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentane acetic dianhydride, bicyclo [2,2,2] octo-7-ene-2,3,5,6- Tetraca 1 type selected from the group consisting of acid dianhydrides, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydrides, 3,5,6-tricarboxy-2-norbornane acetic dianhydrides and derivatives thereof It is the above-mentioned tetravalent organic group, The photosensitive resin composition characterized by the above-mentioned.
The method of claim 1,
Y ₁ of the polyimide represented by Formula ₁ Silver 3,5-diaminobenzotrifluoride, 2,2'-bis (trifluoromethyl) -4,4'-diamino biphenyl, 2,2-bis [4- (amidophenoxy) phenyl ] Photosensitive resin composition characterized in that it is a divalent organic group containing one or more fluorine elements selected from the group consisting of hexafluoropropane and 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane. .
The method of claim 1,
Y ₂ and Y ₃ of the polyimide represented by Formulas 1 and 2 are respectively

Diamine containing a hydroxyl group selected from the group consisting of;

Diamine containing a carboxyl group represented by;
3,5-diaminobenzotrifluoride, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2-bis [4- (aminophenoxy) phenyl] hexa Fluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 3,5-diaminobenzoic acid, p-phenylenediamine, m-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4 -Phenylenediamine, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, 3,3'-diaminodiphenylether, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-methylene-bis (2-methylaniline), 4, 4'-methylene-bis (2,6-dimethylaniline), 4,4'-methylene-bis (2,6-diethylaniline), 4,4'-methylene-bis (2-isopropyl-6-methyl Aniline), 4,4'-methylene-bis (2,6-diisopropylaniline), 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, benzidine, o-tolidine , m-tolidine, 3,3 ', 5,5'-tetramethylbenzidine, 2,2'-bis (trifluoromethyl) benzidine, 1,4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy Phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 2,2-bis [4- (3 Aromatic diamine selected from the group consisting of -aminophenoxy) phenyl] propane; And
1,6-hexadiamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 4,4 At least one diamine selected from the group consisting of '-diaminodicyclohexylmethane and 4,4'-diamino-3,3'-dimethyldicyclohexylmethane; Resin composition.
The method of claim 1,
E ₁ to E ₄ of the polyimide represented by Formulas 1 and 2 are 4-aminophenol, N- (4-aminophenyl) maleimide, 4-ethynylaniline, maleic anhydride, 5-norbornene- 1 type selected from the group consisting of 2,3-dicarboxylic acid anhydride, 1,2-cyclohexanedicarboxylic acid anhydride, n-octylsuccinic anhydride, 4-thiolaniline, 4-phenylethynyl phthalic anhydride, and the like. It is the above polymer terminal, The photosensitive resin composition characterized by the above-mentioned.
The method of claim 1,
The photoactive compound is an o-quinone diazide derivative, 1,2-naphthoquinone diazide derivative, allyl diazonium salt, diallyl iodonium salt, triallylsulfonium salt, o-nitrobenzyl ester, p-nitrobenzyl ester, tri A photosensitive resin composition comprising a halomethyl group-substituted s-triazine derivative, an imidesulfonate derivative and at least one compound selected from the group consisting of

E ranges from 1 to 1000 in repeat units.
The method of claim 10,
The condensation reaction compound is a photosensitive resin composition, characterized in that at least one selected from the group consisting of:

E ranges from 1 to 1000 in repeat units,
Where -OD is each

And -OH.
The method of claim 1,
The photosensitive resin composition is N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine , Dimethyl sulfone, hexamethyl sulfoxide, m-cresol, γ-butyrolactone, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, butyl carbitol acetate, ethylene glycol, A photosensitive resin composition comprising at least one solvent selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, butyl lactate, cyclohexanone, and cyclopentanone.
The method according to any one of claims 1 to 12,
The photosensitive resin composition further comprises at least one other additive selected from the group consisting of a curing agent, a dissolution rate regulator, a sensitizer, an adhesion enhancer, and a surfactant in the photosensitive resin composition.
The photosensitive film formed using the photosensitive resin composition of any one of Claims 1-12.
The method of claim 14,
The thickness of the photosensitive film is a photosensitive film, characterized in that 1 to 20㎛.
The method of claim 14,
The photosensitive film may include an interlayer insulating film, a passivation film, a buffer coat film, an insulating film for multilayer printed circuit boards, an insulating film for OLEDs, a protective film for thin film transistors for liquid crystal display devices, an electrode protective film for organic EL devices, and the like. A photosensitive film, characterized in that it is used for at least one selected from the group consisting of a semiconductor protective film.