KR20110051688A

KR20110051688A - A positive photosenstive polyimide resin composition

Info

Publication number: KR20110051688A
Application number: KR1020090108403A
Authority: KR
Inventors: 송인각; 진영준
Original assignee: 동우 화인켐 주식회사
Priority date: 2009-11-11
Filing date: 2009-11-11
Publication date: 2011-05-18

Abstract

The present invention (a) an additive comprising a crosslinking photosensitive agent; (b) alkali soluble polyimide resins; (c) a photosensitizer comprising a naphthoquinone diazide compound; And (d) relates to a positive photosensitive polyimide resin composition comprising 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 crosslinking 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 (a) an additive comprising a cross-linking photosensitive agent represented by the formula (1); (B) an alkali-soluble polyimide resin comprising a structural unit represented by Formula 2 and a structural unit represented by Formula 3; (c) a photosensitizer comprising a naphthoquinone diazide compound; And (d) it provides a positive photosensitive polyimide resin composition comprising a solvent.

In Chemical Formulas 1 to 3,

R ₁ to R ₃ are each independently fluorine, chlorine, bromine, iodine, C ₁ to C ₁₈ alkyl group, C ₁ to C ₁₈ hydroxyalkyl group, C ₁ to C ₁₈ alkoxy group, carboxyl group, C ₁ to C ₁₈ alkoxycarbonyl groups, C ₁ to C ₁₈ alkoxycarbonyl groups substituted with C ₁ to C ₁₈ alkoxy groups, C ₁ to C ₁₈ alkyl groups substituted with amino groups, C ₆ to C ₁₈ aryl groups substituted with hydroxy groups, A phenyl group unsubstituted or substituted with one or two or more selected from the group consisting of C ₆ to C ₁₈ arylmercapto groups, C ₁ to C ₁₈ alkylmercapto groups, cyano groups, hydroxy groups, acetoxy groups and nitro groups ; C _{6 Through} C ₁₈ An aryl group; C ₁ to C ₁₀ alkylcarbonyl groups; A C ₃ to C ₁₈ cyclic alkyl group unsubstituted or substituted with an oxo- group; Or a C ₁ to C ₁₀ linear alkyl group unsubstituted or substituted with an oxo- group,

A is MF ₆ , M is P, Sb or As,

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 repeating units, where l is greater than 0 and less than 200, m is greater than 0 and less than 400, and l / m is greater than 0 and less than 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) an additive; (b) alkali soluble polyimide resins; (c) photosensitizers; And (d) a solvent.

The additive (a) contained in the positive photosensitive polyimide resin composition of the present invention includes a crosslinking photosensitive agent represented by the following general formula (1).

In Chemical Formula 1,

R ₁ to R ₃ are each independently selected from F, Cl, Br, I, C ₁ to C ₁₈ Al kilgi, C ₁ to C ₁₈ hydroxyalkyl group, C ₁ to C ₁₈ alkoxy group, a carboxyl group, C ₁ to the in for C ₁₈ alkoxycarbonyl group, C ₁ to about a C ₁ to C ₁₈ alkoxy group, an amino group, a C ₆ to C ₁₈ substituted with a hydroxy group substituted with an alkyl group of C ₁ to C ₁₈ substituted with an alkoxycarbonyl group of C ₁₈ aryl group Substituted or unsubstituted with one or two or more selected from the group consisting of C ₆ to C ₁₈ aryl mercapto groups, C ₁ to C ₁₈ alkyl mercapto groups, cyano groups, hydroxy groups, acetoxy groups and nitro groups Phenyl group; C _{6 Through} C ₁₈ An aryl group; C ₁ to C ₁₀ alkylcarbonyl group; A C ₃ to C ₁₈ cyclic alkyl group unsubstituted or substituted with an oxo- group; Or a C ₁ to C ₁₀ linear alkyl group unsubstituted or substituted with an oxo- group,

A is MF ₆ and M is P, Sb or As.

The additive containing the crosslinking type photosensitive agent represented by the above (a) formula (1) allows the positive photosensitive polyimide resin composition of the present invention to have high sensitivity and high resolution.

The additive containing the cross-linking photosensitive agent represented by the formula (a) is based on 100 parts by weight of the alkali-soluble polyimide resin comprising a structural unit represented by the formula (3) and a structural unit represented by the formula (3) to be described later , 0.01 parts by weight to 20 parts by weight is preferably included, more preferably 0.1 to 10 parts by weight. If the above-mentioned range is satisfied, the phenomenon that the resolution is reduced at high sensitivity can be suppressed.

The sulfonium cation preferable as the crosslinking photosensitive agent represented by Chemical Formula 1 is as follows.

The sulfonium cation is triphenylsulfonium, 4-hydroxyphenyldiphenylsulfonium, (4-tert-butylphenyl) diphenylsulfonium, bis (4-tert-butylphenyl) phenylsulfonium, tris (4- tert-butylphenyl) sulfonium, 4-methylphenyldiphenylsulfonium, bis (4-methylphenyl) phenylsulfonium, tris (4-methylphenyl) sulfonium, (4-tert-butoxyphenyl) diphenylsulfonium, bis (4-tert-butoxyphenyl) phenylsulfonium, tris (4-tert-butoxyphenyl) sulfonium, (3-tert-butoxyphenyl) diphenylsulfonium, bis (3-tert-butoxyphenyl) Phenylsulfonium, tris (3-tert-butoxyphenyl) sulfonium, (3,4-ditert-butoxyphenyl) diphenylsulfonium, bis (3,4-ditert-butoxyphenyl) phenylsulfonium , Tris (3,4-ditert-butoxyphenyl) sulfonium, diphenyl (4-thiophenoxyphenyl) sulfonium, (4-tert-butoxycarbonylmethyloxyphenyl) diphenylsulfonium, tris (4-tert-butoxycarbonylmethyloxyphenyl) sulfonium, (4-tert-butoxyphenyl) bis (4-dimethylaminophenyl) sulfonium, Lis (4-dimethylaminophenyl) sulfonium, tris (4-methoxyphenyl) sulfonium, tris (4-ethoxyphenyl) sulfonium, 2-naphthyldiphenylsulfonium, dimethyl-2-naphthylsulfonium, 4 -Hydroxydiphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, dimethylphenylsulfonium, diphenylmethylsulfonium, trimethylsulfonium, 2-oxocyclohexylcyclohexylmethylsulfonium, 2-oxocyclohexyl -Methyl-phenylsulfonium, 2-oxocyclopentyl-methyl-phenylsulfonium, 2-oxopropyl-methyl-phenylsulfonium, tribenzylsulfonium, tris (p-tolyl) sulfonium, benzylmethyl (p-hydride It is preferable that it is 1 type, or 2 or more types chosen from the group which consists of oxyphenyl) sulfonium, benzyl methyl (p-acetoxyphenyl) sulfonium, and methyl (p-hydroxyphenyl) (o-methylphenyl) sulfonium. Among them, triphenylsulfonium, tris (p-tolyl) sulfonium, benzylmethyl (p-hydroxyphenyl) sulfonium, benzylmethyl (p-acetoxyphenyl) sulfonium, methyl (p-hydroxyphenyl) (o-methylphenyl) sulfonium, 4-tert-butoxyphenyldiphenylsulfonium, diphenylmethylsulfonium, dimethylphenylsulfonium, 4-tert-butylphenyldiphenylsulfonium or tris (4-methylphenyl) sulfonium More preferred is tris (4-tert-butylphenyl) sulfonium, and tris (p-tolyl) sulfonium, benzylmethyl (p-acetoxyphenyl) sulfonium and benzylmethyl (p-hydroxyphenyl) sulfonium Even more preferred, benzylmethyl (p-hydroxyphenyl) sulfonium is most preferred.

(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).

In Chemical Formulas 2 and 3,

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

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.

The X is not particularly limited as long as it is a divalent organic group constituting the diamine and not soluble in aqueous alkali solution, but constitutes a diamine having one or two or more groups selected from the group consisting of phenolic hydroxyl groups, thiophenol groups and sulfonic acid groups. Divalent organic groups; And it is preferable that it is 1 type, or 2 or more types of group chosen from the group which consists of a divalent organic group comprised with the siloxane containing diamine represented by following formula (4).

In Chemical Formula 4,

R ₄ and R ₉ are each independently a C ₁ -C ₅ alkyl group, a compound containing a benzene ring, a cycloorganic compound, R ₅ to R ₈ are each independently a C ₁ to C ₃ alkyl group, n is 1 To 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 preferable that it is 1 type, or 2 or more types selected from the group which consists 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 (4) 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 photosensitive agent containing the (c) naphthoquinone diazide type compound contained in the positive photosensitive polyimide resin composition of this invention makes a positive photosensitive polyimide resin composition of this invention have high sensitivity and high resolution.

The photosensitive agent (c) comprising a naphthoquinone diazide compound is based on 100 parts by weight of an alkali-soluble polyimide resin comprising the structural unit represented by the formula (2) and the structural unit represented by the formula (3). It is preferably included in parts by weight to 75 parts by weight. If it is less than the above-mentioned range, a pattern will be hard to be formed and the problem that most alkali-soluble polyimide resin melt | dissolves may arise. If the above-mentioned range is exceeded, a scum or the like may exist between the patterns, or the pattern may collapse after curing.

The photosensitive agent comprising the (c) naphthoquinone diazide compound is not particularly limited as long as it is used in the technical field of the present invention. Substances prepared by conventional methods of condensation reaction with a hydroxyl group-containing compound can be used. The hydroxy group-containing compound is not particularly limited, but hydroquinone, resorcinol, phloroglucin, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,3,3 ', Tetrahydroxybenzophenones such as 4-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone and 2,2 ', 4,4'-tetrahydroxybenzophenone; And / or pentahydroxybenzophenones such as 2,3,3 ', 4,4'-pentahydroxybenzophenone and 2,3,3', 4,5'-pentahydroxybenzophenone, alkyl gallates and It is preferred that they are the same hydropraban.

The solvent (d) 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 comprising (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 (d) 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-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, One or more selected from the group consisting of cresol, xylenol, chlorophenol, ethylene glycol, diethylene glycol, triethylene glycol, glyme, diglyme, triglyme, gamma-butyrolactone and propylene carbonate It is preferable. Among them, it is preferable to use a mixture of two or more selected from the group consisting of dimethylformamide, N-methylpyrrolidone, dimethylacetamide, butyrolactone and propylene carbonate.

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 alkali-soluble polyimide resin comprising the structural unit represented by the formula (2) and the structural unit represented by the formula (3) and the solvent (d). 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 on the substrate, the layer comprising the forged photosensitive polyimide resin composition of the present invention; (ii) exposing the layer formed in (i) to light having a wavelength of 200 to 700 nm through a photomask on 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 Polyimide Resin

First, 0.5 ml of 1,3-diamino-4-carboxybenzene and 0.5 mmol of 4,4-diaminodiphenyl ether were added to a 100 ml round flask with nitrogen, and N-methyl-2-pyrrolidone was added. 10 mmol (hereinafter, referred to as NMP) was added thereto and dissolved. After the diamine is completely dissolved, 1 mmol of 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride is added and reacted for 2 hours. Then, 0.4 mmol of phthalic anhydride is added and reacted in an ice bath for 24 hours. Polyamic acid was synthesized. 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, followed by reaction for 6 hours while maintaining 60 ° C. in a water bath to proceed with chemical imidization. After cooling to room temperature, the solution was reprecipitated three 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 solid.

The polyimide solid 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

And Y is

R is H, l is 0.5, m is 0.5 and l / m is 1.

As a result of this IR spectral analysis, no absorption derived from the polyamic acid was observed, but absorption based on the imide group was observed at 1780 cm ⁻¹ and 1720 cm ⁻¹ , and derived from the carboxy group in 1 H-NMR spectral analysis. A peak of 11-12 ppm was observed. In addition, the gel permeation chromatography (GPC) analysis of the polyimide solid using HP1200 (trade name, manufacturer: Agilent) showed that the weight average molecular weight (Mn) in terms of polystyrene was 3,200.

Examples 1 to 6, comparative examples 1 to 5: 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 additive and the photosensitizer are described in parts by weight based on 100 parts by weight of the alkali-soluble resin, and the solvent is described in parts by weight based on 100 parts by weight of a solution composed of the alkali-soluble resin and the solvent.

additive
(Parts by weight) Alkali-soluble resin
(Parts by weight) Photosensitizer (parts by weight) Solvent (part by weight) Example 1 S-1 0.05 Synthesis Example 1 100 C-1 40 DMF / GBL / PC: 90/5/5 200 Example 2 S-1 0.1 Synthesis Example 1 100 C-1 40 DMF / GBL / PC: 90/5/5 200 Example 3 S-1 1.0 Synthesis Example 1 100 C-1 40 DMF / GBL / PC: 90/5/5 200 Example 4 S-1 3.0 Synthesis Example 1 100 C-1 40 DMF / GBL / PC: 90/5/5 200 Example 5 S-1 5.0 Synthesis Example 1 100 C-1 40 DMF / GBL / PC: 90/5/5 200 Example 6 S-1 10.0 Synthesis Example 1 100 C-1 40 DMF / GBL / PC: 90/5/5 200 Comparative Example 1 - - Synthesis Example 1 100 C-1 40 DMF / GBL / PC: 90/5/5 200 Comparative Example 2 S-1 20.0 Synthesis Example 1 100 C-1 40 DMF / GBL / PC: 90/5/5 200 Comparative Example 3 I-1 1.0 Synthesis Example 1 100 C-1 40 DMF / GBL / PC: 90/5/5 200 Comparative Example 4 I-1 5.0 Synthesis Example 1 100 C-1 40 DMF / GBL / PC: 90/5/5 200 Comparative Example 5 I-1 10.0 Synthesis Example 1 100 C-1 40 DMF / GBL / PC: 90/5/5 200

S-1: sulfonium cation (SI-100L, manufactured by SANSHIN Chemical Industry)

I-1: Iodonium cation (SP-201, SMC manufacture)

C-1: with 2,6-bis [4-hydroxy-3- (2-hydroxy-5-methylbenzyl) -2,5-dimethylbenzyl] -4-methylphenol having a reaction molar ratio of 1: 2.2. Condensate of 1,2-naphthoquinonediazide5-fonyl chloride (powder form)

DMF: Dimethylformamide

GBL: γ-butyrolactone

PC: Propylene Carbonate

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

The positive photosensitive polyimide resin compositions of Examples 1 to 6 and Comparative Examples 1 to 5 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 was observed a line width of 5 to 20㎛ at a film thickness of 5㎛.

Compound components Effective Sensitivity (msec) Resolution (μm) Example 1 740 (○) 8 (○) Example 2 700 (○) 8 (○) Example 3 620 (○) 7 (○) Example 4 590 (◎) 5 (◎) Example 5 550 (◎) 4 (◎) Example 6 510 (◎) 7 (○) Comparative Example 1 1320 (X) 8 (△) Comparative Example 2 520 (◎) 9 (X) Comparative Example 3 1000 (X) 10 (X) Comparative Example 4 940 (X) 9 (X) Comparative Example 5 890 (△) 9 (X)

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

Resolution (μm) = resolution at target value between 5 and 20 μm

Effectiveness: ◎: Very good, ○: Excellent, △: Normal, X: Poor

Resolution: ◎: Very good, ○: Excellent, △: Normal, X: Poor

Referring to Table 1, the photoresist pattern using the compositions of Examples 1 to 6 has excellent efficacy and resolution, whereas the composition of Comparative Example 1 has an effective sensitivity, Comparative Example 2 has a resolution, and Comparative Example 3 to 5 showed worse results than Examples in terms of effectiveness and resolution.

Claims

(A) an additive comprising a crosslinking photosensitive agent 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;

(c) a photosensitizer comprising a naphthoquinone diazide compound; And

(d) a positive photosensitive polyimide resin composition comprising a solvent:

In Chemical Formulas 1 to 3,

R ₁ to R ₃ are each independently fluorine, chlorine, bromine, iodine, C ₁ to C ₁₈ alkyl group, C ₁ to C ₁₈ hydroxyalkyl group, C ₁ to C ₁₈ alkoxy group, carboxyl group, C ₁ to C ₁₈ alkoxycarbonyl groups, C ₁ to C ₁₈ alkoxycarbonyl groups substituted with C ₁ to C ₁₈ alkoxy groups, C ₁ to C ₁₈ alkyl groups substituted with amino groups, C ₆ to C ₁₈ aryl groups substituted with hydroxy groups, A phenyl group unsubstituted or substituted with one or two or more selected from the group consisting of C ₆ to C ₁₈ arylmercapto groups, C ₁ to C ₁₈ alkylmercapto groups, cyano groups, hydroxy groups, acetoxy groups and nitro groups ; C _{6 Through} C ₁₈ An aryl group; C ₁ to C ₁₀ alkylcarbonyl group; A C ₃ to C ₁₈ cyclic alkyl group unsubstituted or substituted with an oxo- group; Or a C ₁ to C ₁₀ linear alkyl group unsubstituted or substituted with an oxo- group,

A is MF ₆ , M is P, Sb or As,

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

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

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),

0.01 to 20 parts by weight of an additive including the cross-linking photosensitive agent represented by Formula (a); And

(C) 1 part by weight to 75 parts by weight of a photosensitive agent including a naphthoquinone diazide compound; And

Positive type photosensitive polyimide resin composition, comprising (d) 100 to 500 parts by weight of the solvent.

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-naphthalenesuccinic acid , 2,3,5-tricarboxycyclopentylacetic acid, bicyclo (2,2,2) octo-7-ene-2,3,5,6-tetracarboxylic acid, tetrahydrofuran-2,3,4 1, 2 or more types selected from the group consisting of, 5-tetracarboxylic acid, butanetetracarboxylic acid, dianhydride thereof and dicarboxylic acid diacid halide 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; And positive type photosensitive polyimide resin composition characterized by the 1 type (s) or 2 or more types chosen from the group which consists of a divalent organic group obtained from the siloxane containing diamine represented by following formula (4):

In Chemical Formula 4,

R ₄ and R ₉ are each independently a C ₁ -C ₅ alkyl group, a compound containing a benzene ring, a cycloorganic compound, R ₅ to R ₈ are each independently a C ₁ to C ₃ alkyl group, n is 1 To 10.