KR20110057756A - A positive photosenstive polyimide resin composition - Google Patents

Abstract

PURPOSE: A positive photosensitive polyimide resin composition is provided to ensure excellent photosensitivity, development, residual film rate, and resolution, and to satisfy adhesion to a film, heat resistance, insulating property, and flexibility. CONSTITUTION: A positive photosensitive polyimide resin composition comprises (a) a photoresist including quinone diazide sulfonate of a multivalent phenol compound represented by chemical formula 1, (b) an alkali-developable polyimide resin including a structure unit represented by chemical formula 2 and a structure unit represented by chemical formula 3, and (c) a solvent.

Description

Positive photosensitive polyimide resin composition {A POSITIVE PHOTOSENSTIVE POLYIMIDE RESIN COMPOSITION}

The present invention relates to a positive photosensitive polyimide resin composition comprising a quinone diazide sulfonate compound of a polyhydric phenol alcohol as a photosensitive agent.

Recently, miniaturization, weight reduction, and high density of various electronic components have been greatly demanded. In line with these trends, the demands placed on the patterning technology and its materials have become more sophisticated. That is, at present, there is a need for a heat-resistant insulating material that has excellent performance in soldering heat resistance, electroless gold plating resistance, substrate adhesion, chemical resistance, and the like while maintaining flexibility compared to the prior art. In response to these demands, it is most important to improve the apparatus as well as to increase the sensitivity of the polyimide resin used as the heat resistant insulating material. If the exposure time can be shortened by making the polyimide resin highly sensitive, an increase in throughput and a resultant increase in yield can be obtained.

However, since the positive photosensitive polyimide resin currently used has lower sensitivity than the negative photosensitive polyimide resin, improvement of the sensitivity is required. The simplest way to reach high sensitivity is to reduce the molecular weight of the polyimide used in the positive photosensitive polyimide. This method can increase the dissolution rate of the photosensitive polyimide resin in the alkaline developer, thereby apparently increasing the sensitivity of the photosensitive polyimide resin. However, when the molecular weight of the polyimide resin is reduced, when the pattern is formed with the composition prepared using the polyimide resin, the heat resistance, which is resistant to heat of the pattern after development, becomes low, and the loss of the film is increased (the thickness of the film Residual rate decrease), the pattern shape is deteriorated, and the difference in the rate at which the exposed portion and the non-exposed portion dissolve in the developer is small, which causes a very serious disadvantage of decreasing the α value. In addition, when the polyimide pattern is softened and flows or deformations occur, the etching dimensions after etching may be wrong, and the dimensions of the etched substrate may be jagged so that the photosensitive polyimide resin may play a required role as a semiconductor thick film. There is no yield, and the yield drops drastically.

Patents have been issued to solve these problems, for example, Korean Patent No. 10-0405301 discloses a photosensitive resin composition comprising a polyimide precursor, a photoacid generator and a solvent. Since the patent uses a polyamic acid resin as a precursor, there is a problem of volume shrinkage caused by a change in molecular structure and removal of some leaving groups when thermal imidization is performed after pattern formation.

Therefore, development of a new polyimide photosensitive resin composition is calculated | required.

An object of the present invention is to provide a positive photosensitive polyimide resin composition having excellent photosensitivity, developability, residual film ratio, resolution, and the like.

It is also an object of the present invention to provide a positive photosensitive polyimide resin composition having a performance that can be sufficiently satisfied even in the adhesion, heat resistance, insulation, flexibility, and the like of a finally formed film.

The present invention provides a photosensitive agent comprising (a) a quinone diazide sulfonate compound of a polyhydric phenol compound represented by the following formula (1); (B) an alkali-soluble polyimide resin comprising a structural unit represented by Formula 2 and a structural unit represented by Formula 3; And (c) a solvent, wherein the positive type photosensitive polyimide resin composition is provided.

<Formula 1>

<Formula 2>

<Formula 3>

In Chemical Formulas 1 to 3,

R ₁ to R ₅ each independently represent a hydrogen atom, C ₁ to a cycloalkyl group or an aryl group of the alkenyl group of the alkyl group of C _4, C ₁ to C _4, C ₁ to C _4, and the minimum of only R ₁ and R ₂ One is not a hydrogen atom,

W ₁ and W ₂ are each independently a tetravalent organic group constituting a derivative of tetracarboxylic acid,

X is a divalent organic group constituting diamine and not soluble in aqueous alkali solution,

Y is a trivalent organic group constituting diamine and soluble in aqueous alkali solution,

R is hydrogen or an alkyl group of C ₁ to C ₃ ,

l and m are the mole fractions of each repeating unit in the polymer chain,

l is 0.1 to 0.9, m is 0.1 to 0.9 and l / m is 0.1 to 1.

The positive photosensitive polyimide resin composition of this invention is excellent in photosensitivity, resolution, insulation, thermal shock, and adhesiveness. Moreover, the positive photosensitive polyimide resin composition of this invention can implement sufficient residual film property at the time of image development. In addition, the positive photosensitive polyimide resin composition of the present invention does not require a high temperature heat treatment process of 300 ° C. or higher, and can also solve the problem of processability at high temperature. In particular, it is possible to remarkably improve the film shrinkage occurring during the high temperature imidization reaction, which has been a problem in the development of photosensitive polyimide using the existing polyamic acid.

Therefore, since the positive photosensitive polyimide resin composition of the present invention has high sensitivity and high resolution, surface protective films, interlayer insulating films, passivation films, electrode protective layers, positive photoresists, and the like for electrical and electronic devices, especially semiconductor devices and display devices, It can be widely used for forming a protective film.

Hereinafter, the present invention will be described in detail.

The positive photosensitive polyimide resin composition of the present invention comprises: (a) a photosensitizer comprising a quinone diazide sulfonate compound of a polyhydric phenol compound; (b) alkali soluble polyimide resins; And (c) a solvent.

(A) Photosensitive agent contained in the positive photosensitive polyimide resin composition of this invention contains the quinone diazide sulfonate compound of the polyhydric phenol compound represented by following General formula (1).

<Formula 1>

In Chemical Formula 1,

R ₁ to R ₅ each independently represent a hydrogen atom, C ₁ to C ₄ alkyl group, C ₁ to C ₄ cycloalkyl group, or an aryl group of the alkenyl group, C ₁ to C ₄ of the a,

Provided that at least one of R ₁ and R ₂ is not a hydrogen atom.

_{Wherein, R 1, R 2, R} 5 is preferably each independently an alkyl group of C ₁ to C ₄ alkyl group it is preferable, and, R ₃ and R ₄ is a hydrogen atom or a C ₁ to C _4. As for the said alkyl group, it is more preferable that it is a methyl group or an ethyl group.

The photosensitive agent containing the quinone diazide sulfonate compound of the polyhydric phenol compound represented by the said (a) Formula (1) improves sensitivity, without reducing heat resistance and film thickness retention of the positive photosensitive polyimide resin composition of this invention.

The photosensitive agent containing the quinone diazide sulfonate compound of the polyhydric phenol compound represented by the formula (1) is alkali-soluble comprising a structural unit represented by the formula (2) and the structural unit represented by the formula (3) to be described later It is preferable to contain 1-75 weight part with respect to 100 weight part of sum total of a polyimide resin and (c) solvent. If included in the above-described range, it is difficult to form a pattern, the problem that most of the alkali-soluble polyimide resin is dissolved may occur. If the above-mentioned range is exceeded, a scum or the like may exist between the patterns, or the pattern may collapse after curing.

It is preferable that the polyhydric phenol compound represented by the said Formula (1) is 1 type chosen from the group which consists of a compound represented by following formula (4)-(6).

<Formula 4>

<Formula 5>

<Formula 6>

The polyhydric phenol compounds represented by Formula 1, Formula 4, Formula 5, and Formula 6 include pyrogalol and ketone compounds in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, and an ion exchange resin having a -SO ₃ H group. It can be synthesized by condensation reaction. Examples of the ketone compound include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cyclohexyl ketone, acetophenone and the like.

In addition, the photosensitive agent containing the quinone diazide sulfonate compound of the polyhydric phenol compound represented by the formula (1) may further include a quinone diazide sulfonate of the polyhydric phenol compound represented by the following formula (7).

<Formula 7>

In Chemical Formula 7,

Of R ₆ to R ₁₀ is a single, R ₆ and R ₇ each independently represent a hydrogen atom, C ₁ to C ₄ alkyl group, C ₁ to a cycloalkyl group of C ₄ alkenyl group, C ₁ to C ₄ or an aryl group, At least one is not a hydrogen atom.

Wherein, R _6, R ₇ or R ₁₀ is more preferably it is preferred, and a methyl group or an ethyl group is an alkyl group of C ₁ to C _4. R ₈ or R ₉ is preferably a hydrogen atom or an alkyl group having ₁ to ₄ carbon atoms, more preferably a methyl group or an ethyl group.

The polyhydric phenol compound represented by Formula 7 is condensation reaction of a ketone compound and resorcinol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, and an ion exchange resin having a -SO ₃ H group. Can be synthesized. Examples of the ketone compound include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cyclohexyl ketone, acetophenone and the like.

 The sulfonation of the phenolic compound can be produced by a known method. For example, esters can be prepared by condensing phenolic compounds with naphthoquinone diazide sulfonyl halides or benzoquinone diazide sulfonyl halides in the presence of a weak alkali such as sodium carbonate. The esterification (sulfonation) ratio of the polyhydric phenol compound represented by Formula 1 is at least 60%, and the esterification ratio of the polyhydric phenol compound represented by Formula 7, which is another phenol compound, is also at least 60%.

The weight ratio of the quinone diazide sulfonate of the polyhydric phenol compound represented by the formula (7) and the quinone diazide sulfonate of the polyhydric phenol compound represented by the formula (1) is preferably 1: 3 to 4: 1, and 1: 2 to 3 It is more preferable that it is: 1.

(B) Alkali-soluble polyimide resin contained in the positive photosensitive polyimide resin composition of this invention contains the structural unit represented by General formula (2), and the structural unit represented by General formula (3).

<Formula 2>

<Formula 3>

In Chemical Formulas 2 and 3,

W ₁ and W ₂ are each independently a tetravalent organic group constituting a derivative of tetracarboxylic acid,

X is a divalent organic group constituting diamine and not soluble in aqueous alkali solution,

Y is a trivalent organic group constituting diamine and soluble in aqueous alkali solution,

R is hydrogen or an alkyl group of C ₁ to C ₃ ,

l and m are the mole fractions of each repeating unit in the polymer chain,

l is 0.1 to 0.9, m is 0.1 to 0.9 and l / m is 0.1 to 1.

Although the derivative of the said tetracarboxylic acid is not specifically limited, It is preferable that they are tetracarboxylic acid, its anhydride, and these dicarboxylic acid diacid halides. The tetracarboxylic acid derivative may be 1,2,4,5-benzenetetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 3,3', 4,4'-benzophenone Tetracarboxylic acid, 4,4 '-(hexafluoroisopropylidene) diphthalic acid, bis (3,4-dicarboxyphenyl) ether, 2,2'-bis (3,4-dicarboxyphenyl) hexafluoro Lopropane, bis (3,4-dicarboxyphenyl) sulfone, cyclobutane-1,2,3,4-tetracarboxylic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1 Naphthalenesuccinic acid, 2,3,5-tricarboxycyclopentylacetic acid, bicyclo (2,2,2) octo-7-ene-2,3,5,6-tetracarboxylic acid, tetrahydrofuran-2, It is more preferable that it is 1 type, or 2 or more types chosen from the group which consists of 3,4,5- tetracarboxylic acid, butanetetracarboxylic acid, its dianhydride, and dicarboxylic acid diacid halide thereof. 3,3'4,4'-biphenyltetracarboxylic acid, 3,3'4,4'-benzophenonetetracarboxylic acid, 2,2-bis (3,4-di) in the tetracarboxylic acid derivative Tetracarboxylic acids such as carboxyphenyl) hexafluoropropane and bis (3,4-dicarboxyphenyl) sulfone and their dianhydrides and their dicarboxylic acid diacid halides are more preferable from the viewpoint of solubility.

X is not particularly limited as long as it is a divalent organic group constituting diamine and not soluble in aqueous alkali solution, but is obtained from diamine having one or two or more groups selected from the group consisting of phenolic hydroxyl group, thiophenol group and sulfonic acid group. Divalent organic group; Or it is preferable that it is a divalent organic group obtained from the siloxane containing diamine represented by following formula (8).

<Formula 8>

In Chemical Formula 8,

R ₁₁ and R ₁₆ are each independently a C ₁ -C ₅ alkyl group, a compound containing a benzene ring, a cyclo organic compound, R ₁₂ to R ₁₅ are each independently a C ₁ to C ₃ alkyl group, n is 1 To an integer of 10. Herein, the compound containing the benzene ring is preferably a benzene group, and the cyclo organic compound is preferably a cyclohexane group.

The diamine having the phenolic hydroxyl group is 1,3-diamino-4-hydroxybenzene, 1,3-diamino-4-carboxybenzene, 1,3-diamino-5-hydroxybenzene, 1,3- Diamino-4,6-dihydroxybenzene, 1,4-diamino-2-hydroxybenzene, 1,4-diamino-2,5-dihydroxybenzene, bis (3-amino-4-hydrate Hydroxyphenyl) ether, bis (4-amino-3-hydroxyphenyl) ether, bis (4-amino-3,5-dihydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) methane, Bis (4-amino-3-hydroxyphenyl) methane, bis (4-amino-3,5-dihydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino -3-hydroxyphenyl) sulfone, bis (4-amino-3,5-dihydroxyphenyl) sulfone, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2 -Bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3,5-dihydroxyphenyl) hexafluoropropane, 4,4'-diamino- 3,3'-Dihi Doxybiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5 '-Dimethoxybiphenyl, 1,4-bis (3-amino-4-hydroxyphenoxy) benzene, 1,3-bis (3-amino-4-hydroxyphenoxy) benzene, 1,4-bis (4-amino-3-hydroxyphenoxy) benzene, 1,3-bis (4-amino-3-hydroxyphenoxy) benzene, bis [4- (3-amino-4-hydroxyphenoxy) phenyl ] Sulfone, bis [4- (3-amino-4-hydroxyphenoxy) phenyl] propane and 2,2-bis [4- (3-amino-4-hydroxyphenoxy) phenyl] hexafluoropropane It is preferably one or two or more selected from the group consisting of.

Diamines having the thiophenol group include 1,3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene, 1,4-diamino-2-mercaptobenzene and bis (4- It is preferable that it is 1 type, or 2 or more types chosen from the group which consists of amino-3- mercaptophenyl) ether 2, 2-bis (3-amino-4- mercaptophenyl) hexafluoro propane.

The diamine having a sulfonic acid group is 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-5-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, bis (4-aminobenzene-3 Group consisting of 4,4'-diaminobiphenyl-3,3'-disulfonic acid and 4,4'-diamino-3,3'-dimethylbiphenyl-6,6'-disulfonic acid It is preferable that it is 1 type, or 2 or more types chosen from.

Moreover, as diamine containing 2 or more types chosen from the group which consists of a phenolic hydroxyl group, a thiol phenol group, and a sulfonic acid group, bis (4-amino-3- carboxy-5-hydroxyphenyl) ether, bis (4-amino- 3-carboxy-5-hydroxyphenyl) methane, bis (4-amino-3-carboxy-5-hydroxyphenyl) sulfone, 2,2-bis (4-amino-3-carboxy-5-hydroxyphenyl) Propane, 2,2-bis (4-amino-3-carboxy-5-hydroxyphenyl) hexafluoropropane and the like, 4,4-methylene-bis (2,6-ethylaniline), 4,4'- Methylene-bis (2-isopropyl-6-methylaniline), 4,4'-methylene-bis (2,6-diisopropylaniline), bis [4- (3-aminophenoxy) phenyl] sulfone, 2 , 2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 4,4'-diamino-3, 3'-dimethyldicyclohexylmethane, 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylmethane, 1,4-bis (4-aminophenoxy) bene , 1,3-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2 , 2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 4,4′-oxydianiline and 5,5′-oxydiisobenzofuran-1,3-dione It is preferable that it is 1 type, or 2 or more types chosen from. As other diamine, 4,4-diaminodiphenyl ether is preferable.

The siloxane-containing diamine represented by the formula (8) can improve the adhesion between the insulating film and the substrate formed of the positive photosensitive polyimide resin composition of the present invention.

Y is not specifically limited as long as it is a trivalent organic group which comprises diamine and is soluble in aqueous alkali solution.

The alkali-soluble polyimide resin (b) may be prepared using a method of synthesizing and dehydrating a polyimide precursor in a reaction of tetracarboxylic dianhydride and diamine. At this time, it is preferable that it is -20 degreeC-150 degreeC, and, as for the reaction temperature of tetracarboxylic dianhydride and diamine, it is more preferable that it is -5 degreeC-100 degreeC. Solvents that can be used in the preparation method include N, N-dimethylformamide, N, N-dimethylacetoamide, N, N-dimethylmethoxyacetoamide, N-methyl-2-pyrrolidone, 1,3-dimethyl 2-imidazolinone, caprolactam, N-methylcaprolactam, dimethyl sulfoxide, dimethyl sulfone, sulfolane, tetramethyl urea, hexamethylphosphoramide, phenol, cresol, xylenol, chlorophenol, ethylene glycol , Diethylene glycol, triethylene glycol, glyme, diglyme, triglyme and the like. Among them, it is preferable to use polar solvents such as N-methyl-2-pyrrolidone and dimethylacetoamide.

Here, in order to convert a polyimide precursor into a polyimide, a polyimide precursor can be heated at 150 degreeC-250 degreeC in a solution state, and can be catalyst imidized. In the case of the catalyst imidization, tertiary amines such as acetic anhydride and triethylamine, pyridine, isoquinoline, imidazole and the like are added to the polyimide precursor solution, and chemical imidization is performed at an arbitrary temperature of 0 ° C to 350 ° C. Can be.

In addition, to remove the water generated by the dehydration ring closure, toluene or xylene may be added to azeotropic dehydration.

The solvent (c) contained in the positive photosensitive polyimide resin composition of the present invention is based on 100 parts by weight of an alkali-soluble polyimide resin including (b) the structural unit represented by the formula (2) and the structural unit represented by the formula (3). , 100 to 500 parts by weight. If it is included below the above-described range, a problem may occur in the solubility and particles may occur. When included in excess of the above-described range, it is difficult to form a desired coating thickness and there is a concern that a problem of film shrinkage occurs during exposure.

The solvent (c) is not particularly limited as long as it is used in the technical field of the present invention, but is N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylmethoxyacetoamide, N-methyl- 2-pyrrolidone, 1,3-dimethyl-2-imidazolinone, caprolactam, N-methylcaprolactam, dimethylsulfoxide, dimethylsulfone, sulfolane, tetramethyl urea, hexamethylphosphoramide, phenol , One or two selected from the group consisting of cresol, xylenol, chlorophenol, ethylene glycol, diethylene glycol, triethylene glycol, glyme, diglyme, triglyme, γ-butyrolactone and propylene carbonate It is preferable that it is above. It is more preferable to mix and use 2 or more types selected from the group which consists of N, N- dimethylformamide, N-methylpyrrolidone, N, N- dimethylacetamide, (gamma) -butyrolactone, and a propylene carbonate. Do.

In addition, the composition of the present invention, additives such as various inhibitors such as surfactants, plasticizers, sensitizers, dyes, other resin components, thermal reaction inhibitors, adhesive improving agents, etc., in addition to the above components, as long as they do not adversely affect the effects of the present invention. It can be used by appropriately adding one or more kinds.

The additive is 0.1 parts by weight to 20 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble polyimide resin (c) containing the structural unit represented by the formula (2) and the structural unit represented by the formula (3). It is preferred to be included.

On the other hand, using the positive photosensitive polyimide resin composition of this invention, a patterned film can be formed in the following process.

The process comprises the steps of: (i) forming a layer comprising the forged photosensitive polyimide resin composition of the present invention on a substrate; (Ii) exposing the layer formed in (iii) to light having a wavelength of 200 to 700 nm through a photomask in which a predetermined pattern is formed; And (iii) dissolving the exposed layer with aqueous alkali solution to obtain a patterned film.

Hereinafter, the present invention will be described in more detail through synthesis examples, examples, and test examples. However, the scope of the present invention is not limited by the following examples and test examples.

Synthesis Example 1 Synthesis of Photosensitive Agent

Pyrogallol (257.3 g) and 36% hydrochloric acid (92.3 g) were added to methanol (280 g) and the mixture was heated to 47 ° C. with stirring to form a homogeneous solution. Acetone (34.8 g) was added dropwise to the solution over 30 minutes, followed by stirring for 8 hours. After completion of the reaction, water (4 L) and ethyl acetate (1.1 L) were added to the reaction mixture and separated. Water (3 L), ethyl acetate (200 mL) and toluene (150 mL) were added to the organic layer, and the mixture was washed with water. The mixture was then washed three times with water (3 L each). The organic layer was concentrated to give an oily yield (103 g). Ethyl acetate (13 g) and toluene (170 g) were added to the oily material, and the obtained product was recrystallized. Thereafter, the crystalline product is dried at 70 DEG C to obtain a dried product (Formula 4, 22.6 g).

<Formula 4>

Subsequently, naphthoquinone- (1,2) -diazide- (2) -5-sulfonyl chloride (24.18 g), the compound represented by the formula (4) (6.64 g), and dioxane were placed in a 300 ml three-neck flask. (150 g) was poured and stirred to dissolve this compound completely. Here, the molar ratio of naphthoquinone- (1,2) -diazide- (2) -5-sulfonylchloride and the compound represented by the formula (4) was 1: 4.5 and the esterification ratio was 90%. Also, the molar ratio is then the molar ratio of phenolic compound to quinone diazide compound.

The flask was then immersed in a water bath to adjust the reaction temperature to 20-25 ° C. and triethylamine (10.0 g) was added dropwise over 30 minutes with stirring. Thereafter, the reaction mixture was further stirred at 20-25 ° C. for 20 hours. After the reaction is completed, the reaction mixture is poured into ion-exchanged water, filtered and dried to obtain a photosensitive material.

Synthesis Example 2: Synthesis of Polyimide Resin

In order to synthesize an alkali-soluble polyimide resin comprising the structural unit represented by the formula (2) and the structural unit represented by the formula (3), 1,3-diamino-4-carboxy was first filled with nitrogen in a 100 ml round flask. 0.5 mmol of benzene and 0.5 mmol of 5,5′-oxydiisobenzofuran-1,3-dione were added thereto, and N-methyl-2-pyrrolidone (hereinafter referred to as NMP) was added thereto and dissolved. After the diamine was completely dissolved, 1 mmol of 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride was added and reacted in an ice bath for 24 hours to synthesize polyamic acid. At this time, the amount of the solvent is not particularly limited as long as the reaction proceeds, but it is preferable to use an amount such that the solid content concentration does not usually exceed 20% by weight. The reaction was carried out at room temperature over 20 hours, preferably 24 hours. Next, 6 mmol of pyridine and 6 mmol of acetic dianhydride were added to the polyamic acid solution, and the reaction was carried out for at least 6 hours, preferably at least 12 hours while maintaining 60 DEG C in a water bath to proceed with chemical imidization. . The solution was cooled to room temperature, reprecipitated several times with water and methanol, and the resulting precipitate was filtered, washed with methanol, and dried under vacuum for 24 hours to obtain a pale yellow polyimide resin as follows.

이고, X는

, Y는

이고, R은 H이고 l은 0.5, m은 0.5 l/m은 1이었다.The polyimide resin includes a structural unit represented by Chemical Formula 2 and a structural unit represented by Chemical Formula 3, wherein W ₁ and W ₂ are

And X is

, Y is

R is H, l was 0.5, and m was 0.5 l / m.

As a result of IR spectral analysis, no absorption derived from polyamic acid was observed, but absorption based on imide groups was observed at 1780 cm ⁻¹ and 1720 cm ⁻¹ , and derived from carboxy group in 1 H-NMR spectrum analysis. Peaks of 11 to 12 ppm were observed. In addition, the number average molecular weight (Mn) of polystyrene conversion was 89,500 as a result of the gel permeation chromatography (GPC) analysis.

Examples 1 to 3, comparative examples 1 to 3: preparation of positive photosensitive polyimide resin composition

Compositions were prepared with the ingredients and contents shown in Table 1. 25 ppm of a silicone-based surfactant (manufactured by Shin-Etsu Co., Ltd., trade name: SH-8400) was added to the composition to improve applicability. The composition to which the surfactant was added was filtered through a tetrafluoroethylene filter having a pore size of 0.1 μm to prepare a photoresist. Here, the photosensitizer described parts by weight based on 100 parts by weight of alkali-soluble resin, and the solvent described parts by weight based on 100 parts by weight of a solution consisting of alkali-soluble resin and a solvent.

Test Example 1: Evaluation of Characteristics of Positive Photosensitive Polyimide Resin Composition

The positive photosensitive polyimide resin compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were applied and prebaked at 90 ° C. for 120 seconds using a spinner. Exposure was performed (using Nikon's NSR-2205i11D) in the absence of storytelling. The development was carried out at 120 ° C. for 180 seconds using a DNS developer, and then developed for 90 seconds with a 2.38% aqueous tetramethylammonium hydroxide solution. The pattern of the prepared resist is shown in Table 1 by observing the line width of 5 to 10㎛ at a film thickness of 5㎛.

Photosensitizer
(Parts by weight) Alkali soluble resin
(Parts by weight) Solvent (part by weight) Effectiveness
(msec) resolution
(Μm) Example 1 Synthesis Example 1 20 Synthesis Example 2 100 DMF / GBL / PC: 90/5/5 200 740 7 Example 2 Synthesis Example 1 40 Synthesis Example 2 100 DMF / GBL / PC: 90/5/5 200 630 6 Example 3 Synthesis Example 1 60 Synthesis Example 2 100 DMF / GBL / PC: 90/5/5 200 510 6 Comparative Example 1 Synthesis Example 1 One Synthesis Example 2 100 DMF / GBL / PC: 90/5/5 200 - - Comparative Example 2 Synthesis Example 1 80 Synthesis Example 2 100 DMF / GBL / PC: 90/5/5 200 - - Comparative Example 3 a-1 20 Synthesis Example 2 100 DMF / GBL / PC: 90/5/5 200 1180 10

a-1: T307-2 (trade name, manufacturer: Sumitomo)

DMF: N, N-dimethylformamide

GBL: γ-butyrolactone

PC: Propylene Carbonate

Effectiveness (ms) = exposure sensitivity at which resolution is expressed

Resolution (μm) = resolution at target value between 5 and 10 μm

Referring to Table 1, the photoresist patterns using the compositions of Examples 1 to 3 had excellent effectiveness and resolution, whereas Comparative Example 1 did not produce a pattern, and in Comparative Example 2, the pattern after curing This collapse caused the pattern formation to fail. Comparative Example 3 also showed worse results than Example in terms of effectiveness and resolution.

Claims (6)

(A) a photosensitizer comprising a quinonediazide sulfonate of a polyhydric phenol compound represented by formula (1); (B) an alkali-soluble polyimide resin comprising a structural unit represented by Formula 2 and a structural unit represented by Formula 3; And (c) a positive photosensitive polyimide resin composition comprising a solvent: <Formula 1>

<Formula 2>

<Formula 3>

In Chemical Formulas 1 to 3, R ₁ to R ₅ are each independently a hydrogen atom, an alkyl group of C ₁ to C _4, C ₁ to C ₄ alkenyl groups, C ₁ to C _4, and a cycloalkyl group or an aryl group, at least one stage R ₁ and R ₂ are Not hydrogen atoms, W ₁ and W ₂ are each independently a tetravalent organic group constituting a derivative of tetracarboxylic acid, X is a divalent organic group constituting diamine and not soluble in aqueous alkali solution, Y is a trivalent organic group constituting diamine and soluble in aqueous alkali solution, R is hydrogen or an alkyl group of C ₁ to C ₃ , l and m are the mole fractions of each repeating unit in the polymer chain, l is 0.1 to 0.9, m is 0.1 to 0.9 and l / m is 0.1 to 1. The method according to claim 1, To 100 parts by weight of the total of the alkali-soluble polyimide resin comprising the structural unit represented by the formula (2) and the structural unit represented by the formula (3) and (c) the solvent, Positive type photosensitive polyimide resin composition comprising (a) 1 to 75 parts by weight of a photosensitive agent containing a quinonediazide sulfonate of the polyhydric phenol compound represented by the formula (1). The method according to claim 1, (B) To 100 parts by weight of an alkali-soluble polyimide resin comprising a structural unit represented by the formula (2) and a structural unit represented by the formula (3), Positive type photosensitive polyimide resin composition containing 100 to 500 weight part of said (c) solvents. The method according to claim 1, A positive photosensitive polyimide resin composition according to claim 1, wherein the polyhydric phenol compound represented by Formula 1 is one selected from the group consisting of compounds represented by Formulas 4 to 6. <Formula 4>

<Formula 5>

<Formula 6>

The method according to claim 1, The derivatives of the tetracarboxylic acid are 1,2,4,5-benzenetetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 3,3', 4,4'-benzo Phenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, bis (3,4-dicarboxyphenyl) sulfone, 3 , 3'4,4'-biphenyltetracarboxylic acid, 3,3'4,4'-benzophenonetetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, Bis (3,4-dicarboxyphenyl) sulfone, cyclobutane-1,2,3,4-tetracarboxylic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene Succinic acid, 2,3,5-tricarboxycyclopentylacetic acid, bicyclo (2,2,2) octo-7-ene-2,3,5,6-tetracarboxylic acid, tetrahydrofuran-2,3, One, two or more selected from the group consisting of 4,5-tetracarboxylic acid, butanetetracarboxylic acid, dianhydrides thereof, and dicarboxylic acid diacid halides thereof The positive photosensitive polyimide resin composition according to claim. The method according to claim 1, X is a divalent organic group obtained from diamine having one or two or more groups selected from the group consisting of a phenolic hydroxyl group, a thiophenol group and a sulfonic acid group; Or a divalent organic group obtained from a siloxane-containing diamine represented by the following formula (8): <Formula 8>

In Chemical Formula 8, R ₁₁ and R ₁₆ are each independently a C ₁ to C ₅ alkyl group, a compound containing a benzene ring, a cyclo organic compound, R ₁₂ to R ₁₅ are each independently an alkyl group of C ₁ to C ₃ , n is an integer of 1 to 10 as a repeating unit.