KR101179123B1 - Photosensitive polyimide-based polymer, and positive type photoresist resin composition comprising the same - Google Patents

Abstract

The present invention relates to a polyimide-based polymer and a positive photosensitive resin composition comprising the same as a binder resin, wherein the photosensitive resin composition of the present invention has high resolution, high sensitivity, excellent film properties, and mechanical properties, which are required characteristics of a semiconductor buffer coating. It has the effect of showing physical properties.

Photosensitivity, photoresist, polyimide, polyamic acid, i-ray, high resolution, high sensitivity

Description

Photosensitive polyimide-based polymer, and positive type photosensitive resin composition comprising the same {Photosensitive polyimide-based polymer, and positive type photoresist resin composition comprising the same}

The present invention provides a photosensitive polyimide polymer comprising a dianhydride having a specific structure in a repeating unit, and using this as a binder resin of a positive photosensitive resin composition, having a high resolution and high sensitivity, and having excellent film properties and mechanical properties. It relates to a polymer and a positive photosensitive resin composition comprising the same.

Recently, in the semiconductor device field mainly on semiconductors and liquid crystal display devices, as the movement of high integration, high density, high reliability, and high speed of electronic devices are rapidly spreading, there is an attempt to take advantage of the advantages of organic materials that are easy to process and high purity. Research is actively underway. However, in order for the organic polymer to be used in these fields, it must be thermally stable even at a temperature of 200 ° C. or higher in the device manufacturing process.

Since polyimide compounds are excellent in thermal stability and excellent in mechanical, electrical, and chemical properties, recently, the use of photosensitive insulating films including photosensitive resins including the same has been extended not only to semiconductors but also to display fields. Therefore, there is a demand for a polyimide polymer compound having no film reduction or swelling in the formation of fine patterns, which was not required in conventional polyimide photosensitive resins.

The polyimide polymer is subjected to two-step condensation polymerization of a diamine component and a dianhydride component in a polar organic solvent such as N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc) and dimethylformamide (DMF). It is generally prepared by obtaining a polyimide precursor solution, coating it on a silicon wafer or glass, and curing it by heat treatment. Commercialized polyimide products for electronic materials are supplied in the form of polyimide precursor solution or polyimide film, and are mainly supplied in the form of polyimide precursor solution in the semiconductor device field.

Polyimide resin is applied to the buffer coating film of a semiconductor element. In a large-scale integrated circuit (LSI), cracks occur in a passivation film of a chip due to shrinkage of the resin after packing and thermal stress due to a difference in the coefficient of thermal expansion between the chip and the resin, or metal wiring. It can also be damaged. In order to solve this problem, a buffer layer made of polyimide is formed between the chip and the encapsulant. The thickness of the buffer layer may be 10 μm or more to play a role, and the thicker the thickness, the better the buffer effect and the higher the yield of semiconductor products. do.

The polyimide layer requires the formation of fine patterns such as interelectrode connections and wire bonding pads. In order to form a via hole in the polyimide layer, a conventional method of coating and etching a photoresist on an existing non-photosensitive polyimide film has been widely used, but recently, a photosensitive polyimide having a photosensitive function in the polyimide itself has been used. There are many attempts to apply. This requires an etching process for processing holes using a separate photoresist for wire bonding and metal interconnects using conventional non-photosensitive polyimide, but lithography with photoresist using photosensitive polyimide Because the process can be omitted, the buffer coating process can be shortened by about 50%, improving productivity and reducing manufacturing costs. In addition, this is because there is an advantage such as shortening the process at the end of the semiconductor device assembly process (assembly process) to greatly improve the production yield.

Recently, however, studies on positive photosensitive polyimides have been actively conducted, rather than such negative photosensitive polyimides.

The reason is that, firstly, it has better resolution than negative photosensitive polyimide, and secondly, since the light irradiation area is relatively smaller than that of negative photosensitive polyimide, third, defects are less likely to occur. In the negative method, since organic solvents such as N-methyl-2-pyrrolidone (NMP) or dimethylacetamide (DMAc) are used as the developer, there are problems in terms of costs and environmental aspects such as wastewater treatment. The positive method using an alkaline aqueous solution is cost-saving and environmentally friendly.

On the other hand, as a method of providing photosensitivity to a polyimide resin so that it can be used for the photosensitive resin composition, chemically bonding a crosslinkable functional group to a polyimide precursor, or mixing a crosslinkable monomer has been used.

For example, the polyamic acid, the polyamic acid ester which has an acidic group in a side chain, or the polyimide added the quinonediazide compound, etc. are mentioned. However, since the polyamic acid has solubility in an alkaline developer is too good, there is a big problem in film reduction during development, it is necessary to add an amine or the like. In addition, the polyimide or polyamic acid ester having an acid group in the side chain is excellent in terms of resolution and the like, but there is a problem that the acid group remains in the polymer even after curing, resulting in high water absorption of the final cured film or lower alkali resistance.

Therefore, there is an urgent need to develop a polyimide compound having an excellent solubility in an alkaline developer and having excellent developability without film reduction or swelling in forming a fine pattern.

In the present invention, while being able to solve the solubility in the alkaline developer having a positive photosensitive resin composition containing a polyimide compound as a binder resin, it is added in the photosensitive resin composition to maintain the resolution, sensitivity, mechanical properties, etc. Is in developing the resin.

Therefore, in the present invention, by including the dianhydride having a specific structure in the repeating unit of the polyimide polymer to produce a polyimide-based polymer, by using it as a binder resin of the photosensitive resin composition, it is possible to solve the above problems.

SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive polyimide polymer having high solubility, high sensitivity, excellent film properties and mechanical properties by being added as a binder resin in a photosensitive resin composition while having a proper solubility in an alkaline developer.

Another object of the present invention is to provide a positive photosensitive resin composition comprising a polyimide polymer having the above characteristics as a binder resin and adding a photoactive compound, a solvent and the like thereto.

The photosensitive resin composition of the present invention has an effect of showing high resolution, high sensitivity, excellent film properties, and mechanical properties, which are required characteristics of a semiconductor buffer coating.

The present invention relates to a photosensitive polyimide polymer and a positive photosensitive resin composition comprising the same as a binder resin.

Hereinafter, the present invention will be described in detail.

1. Polyimide Polymer

The photosensitive polyimide polymer of the present invention is represented by the following formula (1).

Formula 1

,

,

, 및

중에서 선택된 것이고, Y2는 2가의 지방족 또는 방향족 유기기이다. In Chemical Formula 1, Z is 1 to 100 mole% of 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxyl, respectively. Tetracarboxylic acid and its derivatives comprising ric anhydride 4- (2,5- (dioxotetrahydrofurane-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (THNDA) A tetravalent organic group, and the repeating unit a is 1 to 150; b is 1 to 400; Y1 and Y2 are divalent organic groups constituting diamine, respectively, and Y1 is

,

,

, And

And Y2 is a divalent aliphatic or aromatic organic group.

The polyimide polymer represented by Chemical Formula 1 is obtained by reacting an organic tetracarboxylic acid or derivative thereof constituting Z with an organic diamine constituting Y1, in particular tetracarboxylic dianhydride (usually "acid anhydride"). ) And organic diamine (commonly referred to as "diamine") to react and polymerize to form a polyimide precursor, which is then dehydrated and closed.

In particular, the polyimide compounds of the present invention must have a suitable solubility in an alkaline developer in order to be used as a binder resin in the photosensitive resin composition. Therefore, in the present invention, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid as the acid anhydride constituting Z is mentioned. It is preferable to include the hydride (THNDA) in 1 ~ 100mole% of the total acid anhydride.

Other acid anhydrides other than THNDA include pyromellitic anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, and 3,3', 4,4'-benzophenonetetracarboxylic dianhydride. Water, 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfontetracarboxylic dianhydride, 2,2-bis (3, 4-dicarboxyphenyl) hexafluoroisopropylidene dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonete lacarboxyl Acid dianhydride, 4,4'-hexafluoroisopropylidenediphthalic anhydride, 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetra Carboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane Tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic Acid dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclo Hexene-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 1,2,3 And aromatic, alicyclic, and aliphatic dianhydrides selected from the group consisting of aliphatic tetracarboxylic dianhydrides such as, 4-butanetetracarboxylic dianhydride.

,

,

, 및

중에서 선택된 치환기인 것이 바람직하다. In addition, in Formula 1, Y1 and Y2 are divalent aliphatic or aromatic organic groups constituting diamine, wherein Y1 is

,

,

, And

It is preferable that it is a substituent selected from.

However, Y2 is not particularly limited as long as it is a divalent aliphatic or aromatic organic group constituting a diamine in a conventional polyimide compound, and specific examples thereof include p-phenylenediamine, m-phenylenediamine, 2,4,6 -Trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenyl Ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylmethane, 3,4'-dididiphenylmethane, 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-diisopropylaniline), 4, 4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, benzidine, o-tolidine, m-tolidine, 3,3 ', 5,5'-tetramethylbenzidine, 2,2' -beast Fluoromethyl) 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, At least one aromatic diamine selected from the group consisting of 2-bis [4- (3-aminophenoxy) phenyl] propane;

1,6-hexanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 4,4 And at least one aliphatic diamine selected from the group consisting of '-diaminodicyclohexylmethane, and 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, and selected from the aromatic and aliphatic diamines. It can mix and use 1 or more types.

The reaction temperature of the acid anhydride and diamine may be selected from 80 to 240 ℃, preferably from 130 to 200 ℃.

In addition, polar solvents used in the reaction of the diamine and the acid anhydride include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone and N-methyl Caprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, m-cresol, γ-butyrolactone and the like are used alone or in combination.

The polyamic acid, which is a precursor of the polyimide thus obtained, is precipitated and separated from a solvent such as methanol and ethanol, recovered and used.

It is preferable that the weight average molecular weight of the polyimide-type polymer represented by the said Formula (1) is 1,000-100,000. In addition, it is preferable that glass transition temperature is 200-400 degreeC.

In addition, the polyimide-based polymer represented by the formula (1) is characterized by having a high transmittance having a transmittance of 70% or more in the i-ray wavelength.

2. Positive photosensitive resin composition

Positive photosensitive resin composition according to the present invention is a photosensitive polyimide-based polymer resin represented by the formula (1) alone; Or 1 to 99 parts by weight of the photosensitive polyimide polymer and 100 parts by weight of the binder resin blended with 1 to 70 parts by weight of the polyamic acid represented by the following Formula 2.

(2)

,

,

,

,

, 및

로 이루어진 그룹으로부터 선택된 1종 이상을 1~100몰%로 함유하고, Y3는 디아민을 구성하는 2가의 유기기이고, c는 5내지 200이다.In the above formula, X is a tetravalent organic group constituting tetracarboxylic acid and its derivatives.

,

,

,

,

, And

It contains 1-100 mol% of 1 or more types chosen from the group which consists of, Y3 is a divalent organic group which comprises a diamine, and c is 5-200.

Further, tetracarboxylic acid constituting X and other acid anhydrides constituting derivatives thereof include 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 Acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoroisopropylidene dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3' , 4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-hexafluoroisopropylidenediphthalic anhydride, 3,3 ', 4,4'-diphenylsulfontetracarboxylic 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 Dissolved dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 5- (2 , 5-dioxotetrahydrofuryl) -3-methyl-3-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-tetrahydrofurante tetracarboxylic dianhydride, 3,5,6-tri Aromatic, cycloaliphatic, and aliphatic dianhydrides selected from the group consisting of carboxy-2-norbornane acetic dianhydride, and aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride; There is this.

It will not specifically limit, if it is a divalent aliphatic or aromatic organic group which comprises said Y3, For example, 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'-diaminodi Phenylether, 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-methylaniline), 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) bene Zen, 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-aminophenoxy) phenyl] propane At least one aromatic diamine selected from the group;

1,6-hexanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 4,4 And at least one aliphatic diamine selected from the group consisting of '-diaminodicyclohexylmethane, and 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, and selected from the aromatic and aliphatic diamines. It can mix and use 1 or more types.

The polyamic acid represented by the formula (2) can be obtained by reacting tetracarboxylic dianhydride constituting X and organic diamine constituting Y3.

The method for obtaining a polyamic acid from the acid anhydride and diamine includes N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, and dimethyl sulfoxide. The reaction temperature is -20 to 150 ° C, preferably -5 in a polar solvent used alone or in combination with a seed, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, m-cresol, γ-butyrolactone, or the like. To 100 ° C.

The repeating unit c of the polyamic acid having the repeating unit represented by Formula 2 is preferably 5 to 200.

The polyamic acid having a repeating unit represented by Formula 2 preferably has an elongation of 40% or more, which reduces deformation and breakage of the semiconductor device due to thermal or mechanical stress applied during semiconductor manufacturing and improves reliability of the semiconductor device. To improve.

A photo active compound (PAC) of the photosensitive resin composition according to the present invention is a compound capable of generating an acid when it receives light, and has a function of generating an acid by a photoreaction to increase solubility in an alkaline developer of a light irradiation part. If it is to be not particularly limited. Specifically, o-quinonediazide compound, allyl diazonium salt, diallyl iodonium salt, triallyl sulfonium salt, o-nitrobenzyl ester, p-nitro benzyl ester, trihalomethyl group substituted s-triazine derivative, and already Desulfonate derivatives and the like, and o-quinonediazide compounds are preferred in view of sensitivity and resolution. Usually, the o-quinonediazide compound is o-quinonediazide sulfonic acid ester or o-quinonediazide obtained by condensation reaction of o-quinonediazide sulfonyl chloride with a compound having a hydroxyl group or a compound having an amino group in the presence of a basic catalyst. Used as sulfonamide.

As o-quinone diazide sulfonic-acid component which comprises the said o-quinone diazide sulfonyl chloride, for example, 1, 2- naphthoquinone- 2-diazide- 4-sulfonic acid, a 1, 2- naphthoquinone- 2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2- diazide-6-sulfonic acid, etc. are mentioned.

It is especially preferable to select and use from the compound represented by a following formula.

The photoactive compound is preferably contained 1 to 50 parts by weight based on 100 parts by weight of the polyimide binder resin.

If necessary, a sensitizer such as perylene, anthracene, thioxanthone, Michler's ketone, benzophenone, and fluorene may be used in combination with the photoactive compound.

In addition, the solvent is not particularly limited as long as it can dissolve the polyimide polymer compound, and examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, and N-. Vinylpyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, m-cresol, γ-butyrolactone, ethyl cellosolve, butyl cellosolve, ethyl Carbitol, butylcarbitol, ethylcarbitol acetate, butylcarbitol acetate, ethylene glycol, ethyl lactate, butyl lactate, cyclohexanone, and cyclopentanone.

The composition of the present invention may further include other additives such as dissolution rate regulators, sensitizers, adhesion enhancers, surfactants in addition to the components mentioned above.

The positive photosensitive polyimide resin composition of the present invention having the specific composition as described above is applied onto a substrate such as a glass substrate by using a conventional method such as spin coating, slit spin coating, roll coating, die coating, curtain coating, It forms through exposure and a development process. Exposure and development processes also use the method used at the time of forming the photosensitive layer using a normal photosensitive resin composition, and are not specifically limited.

In the said exposure process, the light source irradiated from the said light irradiation means is not specifically limited, Electromagnetic waves, visible light from an ultraviolet-ray, an electron beam, X-rays, a laser beam etc. are mentioned.

The method of irradiating light by the light irradiation means is not particularly limited, and may be a method of irradiating with a known light source such as a high pressure mercury lamp, a xenon lamp, a carbon arc lamp, a halogen lamp, a cold cathode tube for a copy machine, an LED, a semiconductor laser, or the like. have.

The said developing process is a process of exposing the said photosensitive layer by the said exposure process, hardening the exposed area | region of the said photosensitive layer, and developing by removing a non-hardened area | region, and forming a pattern.

The developing solution is not particularly limited, and examples thereof include hydroxides or carbonates of alkali metals or alkaline earth metals, aqueous solutions of hydrogen carbonate, ammonia water, and quaternary ammonium salts. Among these, KOH aqueous alkali solution is especially preferable.

The developer includes a surfactant, an antifoaming agent, an organic base (for example, benzylamine, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.); In order to promote the development, an organic solvent (for example, alcohols, ketones, esters, ethers, amides, lactones, etc.) may be used in combination. 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 a spin coating of the photosensitive composition on a substrate and prebake at about 100 ° C. for 2 minutes to form a film. After exposing the film with an energy of 100-200 mJ / cm 2 under a high-pressure mercury lamp using a photomask, the pattern is developed using an aqueous KOH aqueous solution and washed with deionized water. After that, postbake was performed at 200 ° C. for about 40 minutes to obtain a pattern.

Thus, the thickness of the photosensitive layer of the present invention may vary depending on the purpose, 1 to 20㎛ is preferred, but is not limited thereto.

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

The positive type photosensitive polyimide 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 OLEDs, but also a protective film for thin film transistors for liquid crystal display devices, and electrodes for organic EL devices. It is preferable to use for a protective film, a semiconductor protective film, etc.

Hereinafter, the present invention will be described in more detail with reference to the following Examples, but the present invention is not limited thereto.

Example 1 Preparation Example of Polyimide Copolymer of 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. 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride 4 while maintaining in water at room temperature 9.0 g of-(2,5- (dioxotetrahydrofurane-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, THNDA) was slowly added. 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 16 g of a soluble polyimide resin.

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

Example 2 Preparation Example of Polyamic Acid Represented by Formula 2

Into a 1 L round bottom jacket reactor, 73.3 g of 4,4'-oxydianiline and 300 g of γ-butyrolactone were sequentially added and slowly stirred to completely dissolve. Then, the jacket temperature of the reactor was maintained at 20 ° C. 3, 55.8 g of 3 ', 4,4'-diphenylsulfontetracarboxylic dionehydride was added slowly and stirred. The mixed solution was stirred for 2 hours to fully react, followed by further stirring at room temperature for 16 hours to prepare a polyamic acid.

The polyamic acid 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 1.6.

Example 3 Preparation Example of Photosensitive Resin Composition (Polyimide Composition)

To 1.6 g of the soluble polyimide synthesized in Example 1, a diazonaptoquinone ester compound (TPPA 320: OD / (OD + OH) = 2/3 is selectively given among OH and OD as a photoactive compound.) 0.5 g, 4 g of a solvent γ-butyrolactone (GBL) were added thereto, stirred at room temperature for 1 hour, and then filtered through a filter having a pore size of 1 μm to prepare a photosensitive composition.

Example 4 Preparation Example of Photosensitive Resin Composition (Polyimide / Polyamic Acid Blending)

8.2g of the soluble polyimide synthesized in Example 1 and 27.5g of the polyamic acid synthesized in Example 4 were mixed to prepare a mixture solution. Then, 4.7 g of the solvent γ-buty was given to the mixture solution as a photoactive compound, diazonaphthoquinone ester compound (TPPA 320: OD / (OD + OH) = 2/3, which is optionally given among OH and OD). 18 g of rockactone (GBL) was added thereto, stirred at room temperature for 1 hour, and then filtered through a filter having a pore size of 1 μm to prepare a photosensitive composition.

Experimental Example

1. Resolution evaluation

The photosensitive compositions of Examples 3 and 4 were spin coated onto a 4 inch silicon wafer, and heated at 120 ° C. for 2 minutes on a hot plate to form a 15 μm thick photosensitive film. After the vacuum-treated silicon wafer was vacuum-bonded to the photomask, the G-line stepper Nikon NSR 1505 G4 was sequentially exposed from 20 mJ / cm 2 to 600 mJ / cm 2 at intervals of 5 mJ / cm 2. 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 slowly heated for about 30 minutes under nitrogen stream, starting at room temperature on a hot plate until reaching 180 ° C, and then held at 180 ° C for 60 minutes, and then until 300 ° C. After slowly heating, the mixture was maintained at 300 ° C. for 60 minutes and heat treated.

The finished film had a thickness of 10 µm and a minimum line width of 3 µm, showing excellent resolution. 1 and 2 are electron micrographs of patterns in which high resolutions of Examples 3 and 4 are implemented.

2. Film property evaluation

The photosensitive composition prepared in Example 3 was spin-coated on a glass plate, and sequentially heat-treated at 180 ° C. for 60 minutes at 300 ° C. and 60 minutes at 300 ° C. under a nitrogen stream to form a polyimide film having a thickness of 10 μm. The film was peeled off the glass plate by performing a pressure cooking treatment (PCT) process for 30 minutes under conditions of 125 ° C. and 2.3 atm in an autoclave. The peeled polyimide film was cut into specimen sizes of 1 cm in width and 8 cm in length, and tensile properties were measured. The results are shown in Table 1 below.

The tensile strength
(Tensile Strengh, MPa) Elongation
(Elongation,%) Modulus
(Modulus, GPa) Example 2 160.4 126.5 2.9 Example 3 105.4 9.8 3.2 Example 4 131.3 30.5 2.9

As shown in the tensile property results of Table 1, when the polyimide according to the present invention is used alone as the binder resin in the photosensitive resin composition, not only the resolution is excellent, but the mechanical properties including tensile strength are also excellent. It can be confirmed that it is excellent. In addition, in the case of Example 4 blended polyimide and polyamic acid was used as the binder resin it was confirmed that the formation of a pattern with improved mechanical properties.

1 and 2 are electron micrographs of the patterns obtained from the compositions according to Examples 3 and 4, respectively.

Claims (9)

A photosensitive polyimide polymer represented by Formula 1 below: Formula 1

In Chemical Formula 1, Z is 1 to 100 mole% of 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxyl, respectively. Tetracarboxylic acid including rick anhydride and a tetravalent organic group constituting the derivative thereof, and the repeating unit a is 1 to 150; b is 1 to 400; Y1 and Y2 are divalent organic groups constituting diamine, respectively, and Y1 is

,

,

, And

Y 2 is a divalent aliphatic or aromatic organic group, 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'-dia Minodiphenylsulfide, 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-methylaniline), 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- S (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4 At least one aromatic diamine selected from the group consisting of -aminophenoxy) phenyl] propane, and 2,2-bis [4- (3-aminophenoxy) phenyl] propane; 1,6-hexanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 4,4 At least one aliphatic diamine selected from the group consisting of '-diaminodicyclohexylmethane, and 4,4'-diamino-3,3'-dimethyldicyclohexylmethane. The photosensitive polyimide polymer according to claim 1, wherein the polyimide polymer has a transmittance of 70% or more at an i-ray wavelength. The photosensitive polyimide polymer according to claim 1, wherein the polyimide polymer has a weight average molecular weight of 1,000 to 100,000 and a glass transition temperature of 200 to 400 ° C. A polyimide-based polymer represented by Chemical Formula 1 according to claim 1 as a binder resin; O-quinonediazide compounds, allyl diazonium salts, diallyl iodonium salts, triallylsulfonium salts, o-nitrobenzyl esters, p-nitrobenzyl esters, trihalomethyl group substituted s-triazine derivatives, imide sulfo Photoactive compounds composed of one or more selected from the group consisting of nate derivatives; And 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, ethyl lactate, lactic acid A positive photosensitive resin composition comprising a solvent composed of one or more selected from the group consisting of butyl, cyclohexanone, and cyclopentanone. The positive type photosensitive resin composition according to claim 4, wherein the binder resin comprises 1 to 70 parts by weight of the polyamic acid represented by the following Chemical Formula 2 in the total binder resin. (2)

In the above formula, X is a tetravalent organic group constituting tetracarboxylic acid and its derivatives.

,

,

,

,

, And

1 to 100 mol% of one or more selected from the group consisting of: Y3 is a divalent organic group constituting diamine, 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'-diamino Diphenylmethane, 4,4'-methylene-bis (2-methylaniline), 4,4'-methylene-bis (2,6-dimethylaniline), 4,4'-methylene-bis (2,6-di Ethylaniline), 4,4'-methylene-bis (2-isopropyl-6-methylaniline), 4,4'-methylene-bis (2,6-diisopropylaniline), 4,4'-diamino Diphenylsulfone, 3,3'-diaminodiphenylsulfone, benzidine, o-tolidine, m-tolidine, 3,3 ', 5,5'-tetramethylbenzidine, 2,2'-bis (trifluor Rommethyl) 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-aminophenoxy) phenyl] propane At least one aromatic diamine selected from the group consisting of: 1,6-hexanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 4,4 At least one aliphatic diamine selected from the group consisting of '-diaminodicyclohexylmethane and 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, c is 5 to 200. The positive type photosensitive resin composition according to claim 5, wherein the polyamic acid represented by Chemical Formula 2 has an elongation of 40% or more and 130% or less. The positive type photosensitive resin composition according to claim 4, wherein the positive type photosensitive resin composition comprises 1 to 50 parts by weight of the photoactive compound and 30 to 90 parts by weight of the solvent, based on 100 parts by weight of the binder resin. The positive type photosensitive resin composition according to claim 4, wherein the photoactive compound comprises at least one compound selected from the following chemical formulas.

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